波长调制-直接吸收光谱(WM-DAS)在线监测大气CO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)可测量吸收率函数和波长调制光谱(WMS)高信噪比的优点,本文首先采用WM-DAS光谱,在50 cm光程和室温低压下,CO分子近红外4300.7 cm^-1谱线吸收率检测限低至4×10^-7(200 s);然后结合120 m长光程Herriott池,在室温大气压下,吸收率函数拟合残差标准差达到5.1×10^-5(1 s).最后利用长光程WM-DAS测量系统,对不同浓度(体积分数为0.44×10^-6—9.6×10^-6)CO进行了动态测量,并将其与腔衰荡光谱(CRDS)进行比较;实验结果表明:本文采用的长光程WM-DAS与CRDS方法测量结果相同,其中长光程WM-DAS系统CO浓度检测限低至0.9×10^-9(200 s),系统简单且测量速度远快于CRDS.与此同时,利用建立的长光程WM-DAS测量系统连续监测1个月时间内大气痕量CO浓度及其变化趋势,测量结果与中国环境监测总站测量结题高度一致.     

Software-switching between direct absorption and wavelength modulation spectroscopy for the investigation of ADC resolution requirements

We present a tunable diode laser spectrometer that can be software-switched between a wavelength modulation spectroscopy (WMS) operation mode and the direct absorption spectroscopy (DAS) technique on a per-scan basis. The new setup allows a direct comparison between the two techniques under equal hardware and system environment conditions. In this work, we compare the impact of analog-to-digital converter resolution for operation in WMS and DAS mode. Example concentration evaluations show that in the DAS approach, relative absorptions smaller than the least significant bit can be measured with scan averaging and FIR-filtering applied. With full resolution, both techniques show similar performance in our setup, with a slight advantage for the WMS implementation.     

TDLAS波长调制压力测量法参数优化

使用TDLAS技术进行动态压力测量已经成为压力测量领域的研究热点。波长调制法实验装置较为复杂,需要对多个参数进行设置,选择出最优的预设参数能够取得更好的实验效果,获得更高的测量精度。目前波长调制法的实验参数设置基本凭借个人经验,使用Matlab程序仿真结合波长调制法的TDLAS测量技术,能够对实验中需要进行预设的重要参数进行了分析。通过计算4990cm-1波段和6330cm-1波段附近的多条吸收峰,发现4990.09cm-1波段处的吸收峰更适合作为波长调制法的测量波段。以4990.09cm-1处的吸收峰为研究对象,进行了波长调制法压力测量仿真建模,计算了调制度、调谐频率和调制频率对二次谐波幅值和对称性的影响并深入地分析了影响因素,总结了其变化规律。在综合考虑抗噪性能和测量精度的情况下,选择了调制度为2.5,调谐频率30Hz,调制频率5kHz为最佳实验参数。基于Matlab的仿真模型能够快速计算大量参数点,更加直观地分析出对参数的影响趋势,为实验仪器和预设参数的选择提供依据。     

基于可调谐二极管激光吸收光谱波长调制技术在线测量燃烧场温度

 介绍了可调谐二极管激光吸收光谱（TDLAS）波长调制技术的测温原理。通过选择水在1 397.75 nm和1 397.87 nm处两条邻近的吸收线,运用多功能数据采集卡对二极管激光器进行控制和信号采集,实现了TDLAS波长调制技术对标定燃烧炉甲烷/空气预混火焰温度的实时在线测量,测量重复频率为250 Hz。分析了温度测量数据抖动的原因,结果表明燃烧过程中火焰本身温度的抖动是测量结果波动的主要原因,测量系统的A类标准不确定度小于53 K。     

Self-calibration wavelength modulation spectroscopy for acetylene detection based on tunable diode laser absorption spectroscopy

The expressions of the second harmonic(2f) signal are derived on the basis of absorption spectral and lock-in theories.A parametric study indicates that the phase shift between the intensity and wavelength modulation makes a great contribution to the 2f signal.A self-calibration wavelength modulation spectroscopy(WMS) method based on tunable diode laser absorption spectroscopy(TOLAS) is applied,combining the advantages of ambient pressure,temperature suppression,and phase-shift influences elimination.Species concentration is retrieved simultaneously from selected 2f signal pairs of measured and reference WMS-2f spectra.The absorption line of acetylene(C_2H_2) at 1530.36 nm near-infrared is selected to detect C_2H_2 concentrations in the range of 0-400 ppmv.System sensitivity,detection precision and limit are markedly improved,demonstrating that the self-calibration method has better detecting performance than the conventional WMS.     

基于可调谐二极管激光吸收光谱波长调制技术在线测量燃烧场温度

介绍了可调谐二极管激光吸收光谱（TDLAS）波长调制技术的测温原理。通过选择水在1 397.75 nm和1 397.87 nm处两条邻近的吸收线,运用多功能数据采集卡对二极管激光器进行控制和信号采集,实现了TDLAS波长调制技术对标定燃烧炉甲烷/空气预混火焰温度的实时在线测量,测量重复频率为250 Hz。分析了温度测量数据抖动的原因,结果表明燃烧过程中火焰本身温度的抖动是测量结果波动的主要原因,测量系统的A类标准不确定度小于53 K。     

Natural logarithm wavelength modulation spectroscopy

Natural logarithm wavelength modulation spectroscopy(ln-WMS) is demonstrated in this Letter. Unlike the conventional wavelength modulation spectroscopy(WMS)-2 f technique, it is a linear method even for large absorbance, which is the core advantage of ln-WMS. The treating method used in ln-WMS is to take the natural logarithm of the transmitted intensity. In order to determine the proper demodulation phase, the η-seeking algorithm is introduced, which minimizes the absolute value of the first harmonic within the non-absorbing region. Subsequently, the second harmonic of the absorption signal is extracted by setting the demodulating phase as 2η. To illustrate the validity of ln-WMS, it was applied to water vapor experimentally. The result shows that even if the absorbance(base-e) is between 1.60 and 6.26, the linearity between ln-WMS-2 f and volume fraction is still established. For comparison, measurement with conventional WMS-2 f was also done, whose response no longer kept linearity. The η values retrieved in continuous measurements and the residuals were shown so as to evaluate the performance of the η-seeking algorithm. Time consumed by this algorithm was roughly 0.28 s per measurement. As an alternative WMS strategy, ln-WMS has a wide range of potential applications, especially where the absorbance is large or varies over a wide area.     

Real-time adaptive noise cancelling for signal-to-noise enhancement in direct absorption spectroscopy

An adaptive filter for cancelling noise contained in the direct absorption spectra is reported. This technique takes advantage of the periodical nature of the repetitively scanned spectral signal, and requires no prior knowledge of the detailed properties of noises. An experimental system devised for measuring CH 4 is used to test the performance of the filter. The measurement results show that the signal-to-noise (S/N) value is improved by a factor of 2. A higher enhancement factor of the S/N value of 5.4 is obtained through open-air measurement owing to higher distortions of the raw data. In addition, the response time of this filter, which characterizes the real-time detection ability of the system, is nine times shorter than that of a conventional signal averaging solution, under the condition that the filter order is 100.     

Multi-mode absorption spectroscopy, MUMAS, using wavelength modulation and cavity enhancement techniques

Multi-mode absorption spectroscopy, MUMAS, has been combined with the techniques of wavelength modulation spectroscopy, WMS, and cavity enhanced absorption spectroscopy, CEAS, to record multiple molecular transitions using a single laser and a single detector. MUMAS signals were recorded using a multi-mode diode laser of the A-band $b^{1}\varSigma _{g}^{+}\leftarrow X^{3}\varSigma _{g}^{-}Multi-mode absorption spectroscopy, MUMAS, has been combined with the techniques of wavelength modulation spectroscopy, WMS, and cavity enhanced absorption spectroscopy, CEAS, to record multiple molecular transitions using a single laser and a single detector. MUMAS signals were recorded using a multi-mode diode laser of the A-band b¹\varSigma _g⁺? X³\varSigma _g^-b^{1}\varSigma _{g}^{+}\leftarrow X^{3}\varSigma _{g}^{-} of molecular oxygen at 760 nm. Direct MUMAS and WMS-MUMAS signals were recorded using a White cell for air and pure oxygen for pressures in the range 0 to 1 bar. CEAS-MUMAS signals were recorded with and without WMS in an open enhancement cavity containing laboratory air. Enhancement of the signal-to-noise ratio has been obtained demonstrating the potential for increased detection sensitivity for gas-sensing applications of MUMAS.     

Multi-harmonic detection in wavelength modulation spectroscopy systems

Two multi-harmonic detection methods for wavelength modulation spectroscopy (WMS) systems are presented and compared. The two possibilities discussed in this paper are: simultaneous curve fitting of multiple harmonic spectra, and reconstruction of the transmission from harmonic coefficients. The optimum number of harmonics is four and 25 harmonics, respectively. Compared with standard single-harmonic curve fitting, the methods give about a factor of 3 better performance than standard second-harmonic curve fitting. Concluding, multi-harmonic detection is better than single-harmonic detection and should be used if the system bandwidth is high enough to allow for proper detection of the higher harmonics.     

非标定波长调制吸收光谱气体测量研究

为消除可调谐激光调制吸收光谱气体测量技术对于标定过程的依赖,研究了二次谐波信号的非标定波长调制气体测量方法.通过对测量的二次谐波线型进行分析,给出相同工况下二次谐波模拟信号,并利用测量与模拟二次谐波信号进行线性拟合直接计算气体浓度.实验室内采用非标定波长调制气体测量方法,利用 6336.24 cm^-1处特征吸收谱线对10 cm长气体吸收池内的CO₂进行了测量.结果表明,非标定波长调制气体测量方法可适应各种不同条件,适合于现场气体在线测量.当调制系数在1.8—3. 关键词： 波长调制 二次谐波 吸收光谱 半导体激光器     

Absorption linewidth inversion with wavelength modulation spectroscopy

For absorption linewidth inversion with wavelength modulation spectroscopy(WMS), an optimized WMS spectral line fitting method was demonstrated to infer absorption linewidth effectively, and the analytical expressions for relationships between Lorentzian linewidth and the separations of first harmonic peak-to-valley and second harmonic zero-crossing were deduced. The transition of CO_2 centered at 4991.25 cm~(-1) was used to verify the optimized spectral fitting method and the analytical expressions. Results showed that the optimized spectra fitting method was able to infer absorption accurately and compute more than 10 times faster than the commonly used numerical fitting procedure. The second harmonic zero-crossing separation method calculated an even 6 orders faster than the spectra fitting without losing any accuracy for Lorentzian dominated cases. Additionally, linewidth calculated through second harmonic zero-crossing was preferred for much smaller error than the first harmonic peak-to-valley separation method. The presented analytical expressions can also be used in on-line optical sensing applications, electron paramagnetic resonance, and further theoretical characterization of absorption lineshape.     

The study of wavelength modulation off-axis integrated cavity output spectroscopy in the case of Lorentzian absorption profile

According to the property of optical cavity and the principle of signals and systems, the mathematical derivations for wavelength modulation off-axis integrated cavity output spectroscopy (WM-OA-ICOS) are presented. And based on the analytical method, the function expression of WM-OA-ICOS signal from Lorentzian absorption profile is obtained. To validate the analyses and deductions, some special cases in 2f-harmonic detection of WM-OA-ICOS are studied and experimented with a built compact WM-OA-ICOS apparatus. It is found that the measured results can coincide with the deduced conclusions. The works can provide some references for the application of WM-OA-ICOS in the case of Lorentzian absorption profile.     

Characterization of lineshape structure by wavelength modulation spectroscopy

Wavelength Modulation Spectroscopy (WMS) is performed in the oxygen A-band at different harmonics for different modulation indices and optical pathlengths. The experimental data is compared to two models with different absorption profiles: one assuming a Lorentzian lineshape function and the other with a Voigt lineshape function. We show that the larger amount of structure in higher harmonic signals provides greater sensitivity to the type of lineshape profile utilized for modeling. A useful new feature explored in this work is optical path length saturation in WMS that was described for the first time in a recent paper from our group. We discuss the role of such saturation and how it can be utilized as a diagnostic to probe lineshape. We also address the effect of the ever present modulation broadening. Results of experiments in which sets of nine scans (direct absorption, 1f, 2f,??,8f; i.e., detection harmonic N=0,1,2,3,??,8) were made simultaneously are described and discussed. Finally, the role that increased structure plays??as a result of increasing order of detection, N, as well as from the modification of the signal profile with increasing optical thickness??is outlined from the perspective of classical information theory.     

High frequency wavelength modulation spectroscopy with diode lasers

High frequency wavelength modulation spectroscopy with diode lasers is accomplished by dithering the drive current at RF frequencies as high as 250 MHz. This technique is useful for fast and sensitive detection of absorption lines in the near-and mid-infrared spectral regions. Detection of 300 MHz wide spectral features corresponding to 1% changes in transmission is accomplished in time intervals as short as 500 ns. A potential application is for fast reading of information contained in frequency domain optical memories based upon photochemical hole burning.     

TDLAS直接吸收法测量CO_2的基线选择方法

本文基于可调谐半导体激光吸收谱线(TDLAS)技术的直接吸收测量,选用中心工作波长为1 580 nm的DFB激光器,在室温及大气常压条件下检测了模拟烟气中的CO_2浓度;采用去峰拟合法和纯N2线拟合法获得基线后反算出了CO_2的浓度,并将反算结果进行了对比。结果表明:采用纯N2线拟合法反算出的浓度的最大相对误差为2.64%,均方值为1.69%;采用去拟合法反算出的浓度的最大相对误差为9.81%,均方值为7.81%。以纯N2吸收谱线作基线的纯N2线拟合方法反算出的浓度的准确度较高,可以为CO_2浓度测量的基线选择提供参考。     

On the wavelength modulation spectroscopy of exciton lines and interference fringes

The lineshape of the wavelength modulation spectra is discussed for the case of strong modulation, when wavelength changes are comparable to the singularity width. Such a procedure is proposed in order to increase the sensitivity of the interference measurements under the weak contrast conditions.     

Measurement of the wavelength modulation indices with selective reflection spectroscopy

The wavelength modulation indices are measured based on harmonic amplitude ratio of 4famp/6famp (4famp and 6famp are the 4- and 6-th harmonic central peak amplitudes correspondingly) with the Doppler-free selective reflection modulation spectroscopy. The experiments for the 6S1/2(F = 4) → 6P3/2(F' = 5) transition of cesium D2 line with 30-MHz linewidth were carried out. The 4f- and 6f-harmonic signals were detected with two digital lock-in amplifiers separately. The maximum error for modulation indices measurement was ±0.1 within the range of m from 3 to 6. The non-linear modulation behaviour of an external cavity diode laser induced by voltage tuning was studied with this method. The method for modulation indices measurement does not require a solid etalon as usual for measuring the wavelength modulation depth and the absorption linewidth correspondingly.     

基于波长调制光谱技术的线宽测量理论及其应用研究

气体吸收谱线的线宽主要包括碰撞作用引起的洛伦兹线宽和分子热运动引起的高斯线宽, 是可调谐二极管激光吸收光谱技术(TDLAS)的重要参数. 本项研究在弱吸收条件下, 通过对波长调制法中二次与四次谐波峰值比进行理论分析和仿真计算, 发现无论洛伦兹和高斯线宽如何变化, 二次和四次谐波峰值比具有恒过不动点的特征. 本文基于该不动点提出了一种线宽在线测量的方法, 并以CO₂分子6982.0678 cm^-1 吸收谱线为例进行实验验证. 实验结果表明, 该方法可以精确测量线宽, 进而根据测量得到的线宽确定气体分压和总压, 可有效地提高TDLAS技术在工业现场中的测量精度.