迭代最小二乘法气体光谱自动水汽差减算法

傅里叶红外光谱法具有测量速度快、信噪比高、检测范围广等优势,在针对污染源废气排放的快速检测及长时间在线监测中具有巨大的发展潜力。水汽是红外光谱污染气体检测中的主要干扰物,影响NO_X,SO₂等重要污染物的检测,差减水汽背景谱消除光谱中水汽干扰可提高这些污染物的检测精度,具有重要意义。气体光谱中水汽吸收峰由于受到水分子团簇、仪器线型函数等影响,通过数值方法对其计算的误差较大;为此,水汽背景谱一般需采用同一台光谱仪实测获得。主要有两种方法： 第一种是通过反复调节水汽/氮气混合气中的水汽浓度,使水汽背景谱中的水汽吸收峰与污染气体光谱中水汽吸收峰相同,此方法耗时较长,且受环境条件制约很难在现场检测中使用;第二种方法是预先测量不同浓度的水汽光谱,在检测污染气体时选取两幅与污染气体光谱中水汽吸收峰最为接近且将其夹在中间的水汽光谱作为参考谱,使用这两幅参考谱线性拟合与污染气体光谱中水汽吸收峰相同的水汽背景谱,此方法可获得高度近似的水汽背景谱,但当前缺乏相关自动算法妨碍了其在快速自动消除水汽干扰方面的应用。为此,提出一种选取水汽参考谱及拟合水汽背景谱的自动算法,用于自动差减消除水汽干扰。在参考谱选取中,使用污染气体光谱依次减去浓度由低至高的水汽光谱,依据差减后光谱中水汽吸收峰所在波数的吸光度正负性来选取参考谱。在水汽背景谱计算中,基于迭代最小二乘法逐步剔除光谱中受污染物吸收峰干扰的波数,采用剩余波数上的数据拟合水汽背景谱,使其与污染气体光谱中水汽吸收峰相一致。使用水汽背景谱对污染气体光谱进行差减即可消除污染气体光谱中的水汽干扰。对含有NO₂的污染气体光谱进行了差减消除水汽干扰实验,结果表明所提出的自动算法可快速准确消除水汽干扰;NO₂在消除水汽干扰后可由其位于1 629 cm-1的强吸收峰检测,相比消除水汽干扰前使用不受水汽干扰的位于2 917 cm-1的弱吸收峰检测,其检出限得到了大幅提高。     

Measurements of O2-broadening and -shifting parameters of water vapor spectral lines in the second hexad region

Oxygen pressure induced broadening and shifting coefficients for water vapor absorption lines in the 8600–9010 cm⁻¹ region have been measured and calculated. The spectra were recorded with a Bruker IFS 125HR spectrometer at a spectral resolution of 0.01 cm⁻¹ for lines with angular moment of the upper states up to 10. Calculations of line broadening and shifting coefficients are performed using a semi-empirical approach. The method is based on the impact theory of broadening, and includes the correction factors whose parameters can be determined by fitting the broadening or shifting coefficients to the experimental data. The comparison of our calculations with the experimental values argues that the semi-empirical method is quite acceptable for the determination of the water vapor absorption line profile parameters.     

基于TDLAS技术的水汽低温吸收光谱参数测量

精确的气体光谱参数对气体浓度、温度等的光谱精确反演测量具有十分重要的意义,针对当前主流光谱数据库(例如HITRAN)中数据与实际数值存在相当误差的问题,自主研制了一套基于静态冷却技术的低温光谱实验平台,用于精确测量低温下的气体吸收光谱参数.运用该低温光谱实验平台,采用可调谐二极管激光吸收光谱(TDLAS)技术测量了温度为230—340 K、压强为10—1000 Pa时7240—7246 cm~(-1)波段的纯水汽振转跃迁光谱.采用Voigt线型多峰拟合方法,获得了5条水汽振转跃迁谱在不同温度、不同压强下的积分吸光度值及洛伦兹展宽值,运用线性拟合的方法得到这5条吸收线的自展宽半峰全宽系数及参考温度下的线强值.运用不确定度传递公式,计算得到实验结果的不确定度,与HITRAN2012数据库中的线参数进行对比,所测的5条吸收线中实验结果与数据库值最大相差10.96%,且实验结果的不确定度为1.11%—2.98%(置信概率p=95%,包含因子k=2),小于HITRAN2012数据库值的不确定度.     

水汽多线光声光谱中压力线位移及加宽系数的分析

本工作从水汽的多线光声光谱中分析得到压力线位移和加宽系数。为了提高系数的精度和拟合效率，采用了Ｖｏｉｇｔ线型和参数分组约束优化方法。     

Comparison between theoretical calculations and high-resolution measurements of pressure broadening for near-infrared water spectra

We report N₂ and air foreign pressure broadening coefficients of more than twenty rovibrational transitions of water vapor in the 935-nm spectral region, and these measurements are compared to new theoretical calculations. The data were obtained using the frequency-stabilized cavity ring-down spectroscopy method, yielding relative uncertainties for the broadening parameters in the range 0.4-2.2%. The sensitivity of measured broadening parameters to the choice of line shape functions is discussed, and systematic differences between experimentally determined collisional broadening coefficients are shown for the cases when the observed line narrowing is interpreted in terms of Dicke-narrowing or the speed-dependence of the collisional broadening and shifting. Theoretical models of pressure broadening for these transitions agree with the measurements to within 4% for most transitions with an average relative difference of 0.63%.     

Pressure broadening coefficients of induced by for Venus atmosphere

Carbon dioxide (CO₂) induced pressure broadening coefficients of water vapor (H₂O) lines have been determined using a terahertz time-domain spectrometer (TDS). Thirty-two rotational transitions of H₂O were observed in the spectral range of 18– (550–3050 GHz) for the first time. Using TDS allows one to measure absorption spectra with one order of magnitude better precision than Fourier transform spectrometer in this frequency region. The precision of our broadening coefficient measurements was 2.4% in average. The measured CO₂ induced pressure broadening coefficients are compared to those calculated by the complex Robert–Bonamy formalism. The difference between the measurement and the theoretical estimation was in the range of -10.7% to +19.0% confirming the credibility of the theoretical approach. The impact on retrieval of water vapor abundance was examined by performing inversion analysis on H₂O spectra of Venus atmosphere obtained with the Submillimeter Wave Astronomy Satellite. In this example case, the retrieved water vapor mixing ratio reduces by half at the altitude region of 70–85 km when applying the newly measured broadening coefficient compared to the air-broadening coefficient, and changes by 5% compared to that estimated by the complex Robert–Bonamy formalism.     

基于代数迭代算法的燃烧火焰温度场和气体浓度场重建研究

基于TDLAS(tunable diode laser absorption spectroscopy)技术,以水汽作为目标气体,采用直接吸收的测量方式,探测了甲烷空气预混平焰炉燃烧区域水汽的吸收光谱信号,通过ART(algebraic reconstruction technique)代数迭代算法对燃烧场温度和水汽浓度分布进行了模拟重建和实验研究,模拟重建采取5×5共25个网格的正方形重建区域,假定25个网格的一个温度浓度二维分布,模拟28条激光束从不同的角度方位穿越重建区域,得到模拟射线下的投影值,经ART算法重建,结果显示温度场和水汽浓度场的重建偏差均在1%以内。实验采用分布反馈式激光器作为光源,选取H₂O的7 153.722,7 153.748和7 154.354 cm-1三条吸收线作为测温谱线,其中前两条线不区分作为一条吸收线来处理。使用平移台多方位平行扫描,共获取30路光谱吸收信号,经数据处理、算法重建和双线比值法测温原理得到了圆形平焰炉16个不同区域的温度浓度值,且炉面偏向中心区域温度浓度值较高,边缘较小,结果表明代数迭代算法能够很好地实现燃烧区域温度场和水汽浓度场的反演。     

Improving spectroscopic line parameters by means of atmospheric spectra: Theory and example for water vapor and solar absorption spectra

Current atmospheric remote sensing experiments measuring high resolution spectra apply instruments of similar quality as the laboratory experiments that are especially equipped to derive spectroscopic parameters. We propose a method that uses high quality atmospheric spectra to improve the spectroscopic parameterization. It is an optimal estimation method that applies the uncertainty ranges given in current spectroscopic databases as a priori covariance and the residuals between the simulated and measured atmospheric spectra as new measurements. We test the method by updating the current HITRAN parameters of 49 mid-infrared water vapor lines (situated in 15 spectral windows between 795 and ) by the information present in high quality ground-based Fourier transform infra-red (FTIR) spectra. We show that the application of a speed dependent Voigt line shape model is important. The updated water vapor parameterization, compared to the original one, leads to lower residuals, larger measurement information content, and better agreement between remotely sensed and coincident in situ water vapor profiles. Using the new line parameterization, a state-of-the-art ground-based FTIR system is able to monitor upper tropospheric water vapor amounts and middle/upper tropospheric HDO/H₂O ratios.     

Measurement of the continuum absorption coefficient of water vapor near 14400 cm−1 (0.694 μm)

The continuum absorption coefficient (CAC) of water vapor (k _cont) in the visible region is determined for the first time from the data of laboratory measurements. For this purpose, the absorption spectra of water vapor in the region 14395–14402 cm^?1 are recorded with the aid of a high-sensitivity photoacoustic spectrometer with a frequency-tunable single-pulse ruby laser, and the absorption measured in this transparency microwindow is compared with that calculated based on the HITRAN 2004 data bank. In the spectral region under study, k _cont = (0.53 ± 0.18) × 10^?9 cm^?1 mbar^?1 at a total pressure of a water vapor-nitrogen mixture of 1000 mbar and a temperature of 295 K. This value of the CAC is roughly 23% higher than the CAC value in the IO-CKD model of the continuum.     

Development of diode laser absorption spectroscopy method for determining temperature and concentration of molecules in remote object

We develop a method of diode laser absorption spectroscopy for noncontact measurements of the temperature and pressure of a gas mixture under unsteady-state conditions at low signal-to-noise ratios. The method is based on the measurement of the absorption spectra of water molecules and approximation of experimental spectra by spectra simulated based on spectroscopic databases. Different approximation algorithms of experimental spectra are tested, such as fitting by individual contours and fitting by a part of the simulated spectrum. We reveal that, at small signal-to-noise ratios, the approximation of experimental data by a simulated spectrum yields more correct data on the temperature of the mixture compared to the fitting by individual contours. For the examined temperature range of 300–1300 K, the determination error of the gas temperature in the test cell proved to be approximately three times lower than upon fitting by individual contours. The developed method of recording and processing spectra is used to measure the temperature, water vapor concentration, and total pressure under the unsteady-state combustion conditions of an air-hydrogen mixture in a supersonic flow.     

不同水体中溶解有机物的荧光光谱特性研究

用激光诱导荧光(laser induced fluorescence, LIF)方法对几种不同水体中溶解有机物(dissolved organic matter, DOM)的荧光光谱进行了测量和分析,给出了不同浓度腐殖酸的归一化荧光强度与浓度的关系。结果表明, 可用此种方法进行有效的水体质量监测。     

基于连续量子级联激光器的1103.4cm–1处NH3混叠吸收光谱特性研究

由于NH3在大气气溶胶化学中具有重要作用,所以快速和精确反演NH3浓度对环境问题非常重要.本文以9.05μm的室温连续量子级联激光器(quantum cascade laser,QCL)作为光源,采用波长扫描直接吸收可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)技术,研究了QCL在1103.4 cm–1的光谱特性,获得了激光器控制的温度电流与波长的关系.设计了QCL二级温控的低压实验平台,测量氨气在1103.4 cm–1处的6条混叠吸收线,在降低压强的情况下谱线展宽变小,使混叠光谱分离,由此计算各条吸收线的线强,进一步对测量不确定度进行分析.针对混叠严重的光谱提出了低压分离单光谱精确反演气体浓度的方法,并进行了实验验证.通过与HITRAN数据库进行结果对比,得出氨气在1103.4 cm–1的实验测量线强值与数据库偏差为2.71%-4.71%,实验测量线强值的不确定度在2.42%-8.92%,极低压条件下反演浓度与实际值的偏差在1%-3%.     

Infrared absorption in dense sodium vapor

The absorption spectra of a dense resonance medium were experimentally studied for the example of thermally heated dense sodium vapor. Several mechanisms that might cause substantial absorption and enhanced intensity of emission in the IR spectral region, λ τ; 0.9 μm, were considered. For the first time, a detailed study of the structure of the absorption spectra of sodium vapor in the specified wavelength range was performed to determine the influence of the kind and pressure of the buffer gas. It was found that buffer gas characteristics had a substantial effect on the absorption coefficient of vapor. The presence of the molecular component (dimers and trimers) in sodium vapor could not explain the experimental dependences of absorption in the infrared region. Possible influence of microparticles formed in condensation of convective sodium vapor flows in heated cells on the optical properties of vapor was considered. Microparticles could contribute to the observed absorption, but were incapable of explaining the substantial intensity of vapor radiation reported earlier. Possible many-particle effects on the absorption in the far spectral line wing were discussed. For the first time, the method of molecular dynamics was used to show for the example of the distribution function of ionic microfields in a dense plasma that such effects were in principle capable of substantially raising the profile of the line and increasing absorption in the region of large detunings from the resonance compared with the simple quasi-static model in the nearest-neighbor approximation.     

Air- and N(2)-Broadening Parameters of Water Vapor: 604 to 2271 cm(-1)

High-resolution measurements of air- and N(2)-broadened widths and pressure-induced frequency shifts of water vapor were obtained covering the spectral region between 604 and 2271 cm(-1). Over 1300 vibration-rotation transitions were measured including the (000)-(000), (010)-(010), (010)-(000), (020)-(010), and (100)-(010) vibrational bands of H(2)(16)O. Also included were measurements of H(2)(18)O and H(2)(17)O from normal water vapor samples and H(2)(18)O + N(2) observations with oxygen-18-enriched gas samples. Collision-narrowing effects were observed in a few lines involving high J and low K(a) transitions with the lowest measured linewidth coefficient equal to 0.0057(4) cm(-1)/atm (air-broadening) for the completely overlapping transitions, 17 0 17 <-- 18 1 18 and 17 1 17 <-- 18 0 18, at 1235.204 cm(-1). The majority of the linewidth values were derived from the measurements using a Voigt line profile. A few lines with air- or N(2)-broadened half-width values of about 0.012 cm(-1) or less were found to exhibit collision-narrowing effects and were also analyzed with a profile proposed by Galatry. The results are compared to values given in previous studies. Copyright 2000 Academic Press.     

光谱地质剖面在蚀变填图中的应用研究

利用遥感数据可以提取与成矿有关的蚀变信息,地质剖面可以为所提取的蚀变信息的验证和深入理解提供依据;结合地质剖面和光谱信息提取的思路提出光谱地质剖面的概念。光谱剖面可以实现光谱沿剖面的存储、显示,而光谱地质剖面的目的主要是得到蚀变类型、矿物含量等参数沿剖面线的分布, 实现蚀变矿物组合空间分带信息的提取。综合现有蚀变信息提取方法建立了光谱地质剖面信息提取的技术方法和流程, 利用地面实测光谱建立了光谱地质剖面,并在光谱地质剖面的支持下利用图像进行蚀变信息的提取和分析,探讨了光谱地质剖面在蚀变分带和遥感找矿模式中的意义和作用,光谱地质剖面的建立有助于图像和地面光谱的一体化分析,有助于蚀变填图中信息的精确提取。     

基于太赫兹时域谱分析的爆炸物检测方法研究

采用太赫兹时域谱分析技术测量了在氮气和空气环境下四种典型爆炸物的太赫兹光谱,并分别利用均值平滑、傅里叶低通滤波以及小波分解与重构三种方法来消除空气中由水蒸气吸收引起的光谱振荡现象。实验结果表明:四种爆炸物的太赫兹光谱具有可分辨的特征,能够作为识别的依据;通过研究水蒸气的影响,使得利用太赫兹时域谱分析技术检测爆炸物向实用化迈进了一步。     

Visualization of acoustic radiation from a vibrating bowling ball.

This paper presents visualization of acoustic radiation from a vibrating bowling ball using the Helmholtz equation least squares (HELS) method. In conducting the experiments, the ball is excited by a vibration shaker using stationary random signals. The radiated acoustic pressures are measured using two microphones and taken as input to the HELS formulations. The reconstructed acoustic pressures on the bowling ball surface are compared with those measured at the same locations. Also shown are comparisons of the reconstructed and measured acoustic pressure spectra at various locations on the bowling ball surface. Results demonstrate that the accuracy of reconstruction based on measurements over a conformal surface is much higher than that over a finite planar surface. This is because the latter often extends beyond the near-field region, making the accuracy of measurements inconsistent. Nevertheless, satisfactory reconstruction of acoustic pressure fields over the entire bowling ball surface can still be obtained based on the measurements taken over a finite planar surface on one side of the source. In a similar manner, the normal component of the surface velocity is reconstructed. Once these acoustic quantities are determined, the time-averaged acoustic intensity is calculated. Also presented are the formulations for estimating a priori the numbers of expansion functions and measurements required by the HELS method and the guidelines for determining the reconstruction error and optimum measurement locations, given the overall dimensions of the source and the highest frequency of interest in reconstruction.     

Measurements of near-IR water vapor absorption at high pressure and temperature

Tunable diode lasers (TDLs) are used to measure high resolution (0.1 cm^-1), near-infrared (NIR) water vapor absorption spectra at 700 K and pressures up to 30 atm within a high-pressure and -temperature optical cell in a high-uniformity tube furnace. Both direct absorption and wavelength modulation with second harmonic detection (WMS-2f) spectra are obtained for 6 cm^-1 regions near 7204 cm^-1 and 7435 cm^-1. Direct absorption measurements at 700 K and 10 atm are compared with simulations using spectral parameters from HITRAN and a hybrid database combining HITRAN with measured spectral constants for transitions in the two target spectral regions. The hybrid database reduces RMS error between the simulation and the measurements by 45% for the 7204 cm^-1 region and 28% for the 7435 cm^-1 region. At pressures above 10 atm, the breakdown of the impact approximation inherent to the Lorentzian line shape model becomes apparent in the direct absorption spectra, and measured results are in agreement with model results and trends at elevated temperatures reported in the literature. The wavelength-modulation spectra are shown to be less affected by the breakdown of the impact approximation and measurements agree well with the hybrid database predictions to higher pressures (30 atm). PACS 33.20.Ea; 42.62.Fi; 52.25.Os     

Simple and highly sensitive optical pulse-characterization method based on electro-optic spectral signal differentiation

A very simple self-referenced, linear pulse-characterization technique based on spectral phase reconstruction by frequency-domain signal differentiation is introduced. This technique can be implemented using electro-optic intensity modulation of the pulse under test with a synchronized RF sinusoid. The pulse spectral phase profile can be accurately and unambiguously reconstructed from only two measured energy spectra, i.e., at the input and at the output of the modulator, using a direct analytic equation. The method is experimentally demonstrated by precisely characterizing microwatt-power picosecond pulses after linear dispersion through short sections (50-700 m) of conventional single-mode fiber.     

基于仪器线型订正的开放光程FTIR测量中的水汽谱在线扣除方法

水汽吸收分布于整个中红外波段,它的存在干扰红外光谱的定量分析。文章介绍了一种从傅里叶变换红外光谱仪的测量数据中扣除水汽干扰信号的新方法。该方法首先通过气象参数测量获得气压、温度和相对湿度,结合HITRAN数据库中提供的水汽线强、自展宽、空气展宽等参数,使用逐线积分方法计算出高分辨率水汽吸收谱,再通过仪器线型订正,合成出与仪器分辨率相匹配的水汽谱,将其作为干扰组分直接从测量所得到的含有水汽的混合光谱中扣除。对开放光程FTIR系统的实测数据的分析结果表明,使用该方法可以有效消除水汽干扰,扣除后的光谱包含待测组分的吸收特征和噪声。在开放光程FTIR等无法使用干燥设备去水的观测条件下,使用该方法可以达到较理想的水汽扣除效果。