Impact of water vapor on 1.51 μm ammonia absorption features used in trace gas sensing applications

Water-vapor-induced pressure broadening is reported for two NH₃ absorption features at 6612.7 and 6596.4 cm⁻¹ that are exploitable for gas sensing applications at atmospheric pressure. Absorption spectra of different NH₃–H₂O–N₂ mixtures were measured at an elevated temperature of 70°C to enable high H₂O concentrations to be reached. Line parameters were determined from a fitting procedure. The significantly greater values obtained for the H₂O-broadening coefficients of the two lines compared to N₂-broadening leads to cross-sensitivity effects in NH₃ trace gas sensors based on spectroscopic techniques that are sensitive to the width of the analyzed absorption line, as is the case in a simple implementation of wavelength modulation spectroscopy or in photoacoustic spectroscopy. In such a case, cross-sensitivity results in inaccurate gas concentration retrieval when the composition of the diluting gas changes. H₂O represents a potentially significant cross-sensitivity source as its concentration may be subject to large variations, especially in high-temperature applications where concentrations up to a couple of tens of percent may be encountered. In contrast to interference which can be minimized by an appropriate choice of the analyzed transitions, cross-sensitivity affects the entire spectrum of the analyte and is thus unavoidable in the mentioned type of gas sensors.     

Diagnostics of a Vibrationally Equilibrium CO2-Containing Gas Mixture at Atmospheric Pressure

A technique is presented for determining the partial pressure and temperature of carbon dioxide in a vibrationally equilibrium gas mixture at atmospheric pressure from experimentally recorded spectra of the absorption coefficient of the lasing lines of a tunable CO₂laser.     

逐线积分气体吸收模型及其在NDIR气体检测中的应用

介绍了一种精确的逐线积分痕量气体吸收模型,模型适用于中红外波段大气环境中痕量气体、污染气体检测的理论研究和工程应用。首先介绍了气体辐射特性的理论计算方法和现有逐线积分大气模 型,比较了各自的优劣性,其次详述了逐线积分计算的理论: 吸收系数是温度、波长、气体浓度和相关吸收线参数的函数,单条谱线的平均吸收系数是积分线强与谱线线型的卷积,在不同的大气条件下选 择不同的线型。最后,详细描述了模型的算法细节,并给出了模型计算的结果与傅里叶变换光谱仪实测数据的对比,举例介绍了吸收模型在NDIR气体探测技术中的实际应用,并使用该模型模拟了NDIR探 测器两个通道的信号强度随尾气中CO₂,CO浓度变化的关系,通过计算确定了NDIR探测器合适的工作范围。所述模型利用HITRAN光谱数据库,考虑了展宽、线翼截断、温度修正、光谱分辨 率变化等情况,可以有效的模拟大气环境中多种气体的红外吸收特征。     

Line shape of the far-wing beyond the band head of the CO2ν3 band

Carbon dioxide is one of the most important trace gases in the terrestrial atmosphere. The spectral data required in remote sensing are the spectral parameter of each absorption line and a line shape model. This paper describes the absorption properties of CO₂ near 2400 cm⁻¹; these properties are of interest to those in the atmospheric temperature sounding field. The shape of the far-wing of N₂- and O₂-broadened CO₂ lines was investigated in the 2200-2500 cm⁻¹ spectral region in a temperature range of atmospheric interest (230-318 K). We focused on the higher rotational quantum number of the R-branch in the ν₃ band, where the effect of the far-wing is enhanced. The effect of the far-wing has been studied extensively by others, since the CO₂ν₃ band is known to exhibit sub-Lorentzian behavior. Here, we show the observed spectra along with calculated spectra for five temperatures. We used first-order line-mixing and the χ-factor, which accounts for the effect of the far-wing, to create the calculated spectra. Our results provide new knowledge of quantum interference of the spectral line in the ν₃ band of CO₂.     

可调谐二极管激光吸收光谱法监测大气痕量气体中的浓度标定方法研究

可调谐二极管激光吸收光谱(TDLAS)技术是利用二极管激光器波长调谐特性,获得被测气体的特征吸收光谱范围内的吸收光谱,从而对污染气体进行定性或者定量分析。在空气痕量气体检测中,一般需要和长光程吸收池相结合使用。可调谐二极管激光吸收光谱法就是在可调谐二极管激光器与长光程吸收池技术相结合的基础上发展起来的一种新的痕量气体检测方法。这种方法不仅精度较高,选择性强而且响应速度快。已经广泛用于大气中多种痕量气体的检测以及地面的痕量气体和气体泄漏的检测。在大部分痕量气体检测仪器中需要精确地对检测气体进行在线的浓度标定,文章介绍了一个简单而精确的浓度标定方法,从理论上进行了分析,然后通过实验证明了这种方法的可行性。     

The limits of signal averaging in atmospheric trace-gas monitoring by tunable diode-laser absorption spectroscopy (TDLAS)

Modern research in atmospheric chemistry requires highly sensitive techniques for the measurement of concentrations of free radicals which determine the rate of photochemical destruction of most atmospheric pollutants. Tunable diode-laser absorption spectroscopy (TDLAS) has already been successfully used for measurements of very low concentrations of stable gases, but further improvement in its sensitivity by signal averaging has been limited by the stability of the instrument. In this paper the concept of the Allan variance is utilized to analyze the stability of an existing frequency-modulated (FM) TDLAS instrument leading to a detection limit for NO₂ of 34 pptv at 6 Hz detection bandwidth. The stability of the instrument allows averaging over 60 s. Taking into account the measuring cycle consisting of the determination of the sample spectra and zero air spectra as well as gas exchange in the absorption cell, the detection limit achievable with this particular instrument was 10 pptv within 25 s under laboratory conditions. Possibilities of further improvement of the detection limit are discussed.     

RING EFFECT: IMPACT OF ROTATIONAL RAMAN SCATTERING ON RADIATIVE TRANSFER IN EARTH’S ATMOSPHERE

One significant limitation to the accuracy of the remote sensing of trace gas constituents in the atmosphere, using UV-visible spectroscopy and scattered sunlight, has often been a reliable knowledge of the so-called Ring effect. In this study it is demonstrated that the filling-in of Fraunhofer and gas absorption features, resulting from Rotational Raman scattering (RRS), explains to high accuracy the Ring effect. A radiative transfer model has been adapted to include RRS and carefully validated by comparison with Ring effect data by other models and from ground-based and satellite data. The analysis of the principle components of the simulated Ring spectra enabled the Fraunhofer and gas absorption filling-in to be separated. This yields a simple, and therefore computational fast, parameterization of the Ring effect suitable for trace gas retrievals. This approach was tested for the retrieval of NO₂ which is considered to be a worst case with respect to absorption feature filling-in for a trace gas retrieved from scattered light. Analysis of the errors in the vertical column of NO₂ derived using differential optical absorption spectroscopy (DOAS) technique indicate that they are dependent on the amount of NO₂ present in the atmosphere when regarding the experimental Ring spectra. This implies that calculated Ring spectra may be superior for DOAS retrievals, compared to the experimentally determined Ring spectra.     

Optical Emission Spectroscopy of Carbon Clusters Produced in a Hollow Cathode Sputter Source

A hollow cathode sputter source is developed to trace the production of carbon clusters and study the influence of discharge current and argon gas pressure on cluster production using an optical emission spectroscopic technique. Optical emission spectra from the hollow cathode source reveal the production of the C₂ Swan band. The sputter source is optimized for the maximum carbon cluster yield. The vibrational temperature analysis of the C₂ cluster is carried out using the Boltzmann plot method. The dependence of vibrational temperature on argon gas pressure is discussed and the dominant method for C-C association in the glow discharge is suggested.     

Investigation on infrared laser absorption spectroscopy measurement of acetylene trace quantities

A laser-based infrared spectrometer was developed for use in high-resolution spectroscopic analysis of trace gases in the atmosphere. Continuous wave, broadly tunable coherent infrared radiation was generated from 8 to 19 μm in a gallium selenide crystal by laser difference-frequency mixing. Measurements of acetylene trace concentrations using laser absorption spectroscopy are reported. The measurements have been performed by using the P(21), Q(11), and R(9) lines of the ν₅ band, respectively, in order to investigate optimal detection conditions: a trade-off choice between higher line absorption strength for sensitive detection and better spectral discrimination from lines overlapping for open path trace-gas monitoring applications. Minimum detectable concentrations are compared under different experimental conditions. The ν₅ R(9) line seems to be close to optimum in terms of absorption strength and freedom from spectral interference for spectroscopic detection of acetylene trace concentration at atmospheric pressure.     

Remote sensing of high temperature H2O-CO2-CO mixture with a correlated k-distribution fictitious gas method and the single-mixture gas assumption

Infrared spectra of high temperature H₂O-CO₂-CO mixtures are calculated using narrow band models in order to simulate hot jet signature at long distance. The correlated k-distribution with fictitious gas (CKFG) approach generally gives accurate data in such situations (especially for long atmospheric paths) but results in long computation time in cases involving mixtures of gases. This time may be reduced if the mixture is treated as a single gas (single-mixture gas assumption, SMG). Thus the lines of the single-mixture gas are assigned to the fictitious gases. In this study, the accuracy of two narrow band models is evaluated. The first narrow band model considers one single-mixture gas and no fictitious gas (CK-SMG) whereas the second model accounts for one single-mixture gas and three fictitious gases (CKFG-SMG). Both narrow band models are compared with reference spectra calculated with a line-by-line (LBL) approach. As expected, the narrow band accuracy is improved by the fictitious gas (FG) assumption particularly when long atmospheric paths are involved. Concerning the SMG assumption, it may lead to an underestimation of about 10% depending on the variation of the gas mixture composition ratio. Nevertheless, in most of realistic situations the SMG assumption results in negligible errors and may be used for remote sensing of plume signature.     

2 μm附近CO2谱线参数测量及应用

吸收光谱技术用于痕量气体浓度监测,特别是在气体分子稳定同位素丰度探测中,吸收谱线参数的准确性非常重要,目前普遍使用的HITRAN数据库中给出的各项参数具有一定的不确定性。为利用2.0 μm激光波段进行CO₂浓度及其同位素丰度探测,需要对该波段的CO₂吸收谱线参数进行校准,采用窄线宽分布反馈式二极管激光器作为光源,结合自行搭建的谱线参数测量系统,采集了2.0 μm波段10条CO₂吸收谱线,获得了各谱线的位置、强度、自加宽系数和N₂加宽系数,并与HITRAN2012数据库中相应的数据进行对比发现两者之间吻合较好,CO₂谱线强度和自加宽系数相对偏差均小于2%。实测实验室大气的CO₂浓度为440 ppm,13CO₂的丰度值δ为-9‰。测量结果为该波段应用于CO₂浓度及13CO₂同位素丰度的实时在线探测提供了重要参考依据。     

Laser-photoacoustic spectroscopy of water-vapor continuum and line absorption in the 8 to 14 μm atmospheric window

This is a comprehensive study of water-vapor line and continuum absorption in the 8–14μm atmospheric window by laser-photoacoustic spectroscopy. The characteristics of laser-photoacoustic spectroscopy and detectors are discussed with results on continuum and line absorption at selected CO₂-laser wavelengths.We have assigned four weak absorption lines which occur at the CO₂-laser emissions 10P(40), 10R(20), 9P(38) and 9R(36) to pure rotational transitions of H₂O, and have determined the dependence of the continuum water-vapor absorption over the temperature range +70°C and −20°C. The measured negative temperature coefficient of the continuum is consistent with both monomer and dimer models, yet not with predictions of larger water clusters.Experiments with supersaturated water vapor indicate that for S ⩾ 1 collision broadening of distant strong lines as well as water dimer absorption contribute to the continuum. However, the dimer absorption is an order of magnitude too small to cause a significant contribution at ambient atmospheric conditions.We have investigated the effect of UV-radiation on the 8–14μm absorption of water vapor, buffered either with N₂ or synthetic air. The observed changes are explained by UV-photodissociation of H₂O molecules and by ozone production. There is no evidence in favor of a cluster model.Finally, we compared our measured spectra with LOWTRAN 6 and HITRAN models. The LOWTRAN yields a stronger negative temperature dependence than observed while the HITRAN does not predict the observed continuum absorption.     

ATMOSPHERIC REMOTE-SENSING REFERENCE DATA FROM GOME: PART 1. TEMPERATURE-DEPENDENT ABSORPTION CROSS-SECTIONS OF NO2 IN THE 231–794 nm RANGE

Absorption cross-sections of NO₂ between 231–794 nm have been measured in the 221–293 K temperature range, using the global ozone monitoring experiment (GOME) flight-model (FM) satellite spectrometer. The spectra have a resolution of about 0.2 nm below 400 nm and of about 0.3 nm above 400 nm. These are the first reference spectra of NO₂ covering at the same time the entire UV–visible–NIR spectral range and a broad range of relevant atmospheric temperatures. The new absorption cross-sections are important as accurate reference data for atmospheric remote-sensing of NO₂ and other minor trace gases.     

Spectral and kinetic features of nonradiative energy transfer in hybrid associates of colloidal quantum dots and organic dyes

We have developed a prototype of a diode-laser absorption spectrometer for noncontact determination of the temperature and concentration of water vapor in the combustion zone of mixed supersonic flows. The method is based on fast scanning of the radiation frequencies of two diode lasers in different spectral ranges containing several absorption lines of water molecules, determining the integral intensities of selected lines, and calculating the medium temperature from the intensity ratio of these lines. The described version of the spectrometer allows one to determine the parameters of the gas medium at high pressures (up to 3 atm) and temperatures (up to 2000 K). The criterion of selection of the spectral scanning ranges of the lasers is described, which is based on minimizing the error of determining the temperature at the expected experimental measurement accuracy of the integral intensities of lines. A program for selection of appropriate combinations of lines from spectroscopic databases has been developed. An algorithm for obtaining the temperature by fitting experimental spectra and theoretical spectra simulated using databases has been developed. Errors of determining the temperature for different fitting algorithms have been estimated. We show that, for the temperature estimation to be more accurate, it is necessary to take into account maximal possible number of lines lying in the scanning ranges of the two lasers.     

可调谐半导体激光吸收光谱遥测二氧化碳通量的研究

可调谐半导体激光吸收光谱技术(TDLAS)具有高分辨率、高灵敏度以及响应时间快等优点.以室温下工作的近红外可调谐半导体激光器为光源,通过波长调制方法对1 578 nm附近CO2气体吸收线的二次谐波信号测量,结合双开放光路技术,实现对不同高度层面700多米长光程范围内CO2气体浓度的快速在线检测.结合大口径闪烁仪测量的莫宁-奥布霍犬长度和特征速度,通过经验公式计算得到CO2气体的通量在-60～60 mg·m-2·s-1范围内波动.实验数据与涡动相关比较表明,两者数据整体变化趋势一致,该方法可以获得较理想的结果.突破了目前对近地面痕量气体通量的监测只能提供局地结果的现象,使大面积范围内痕量气体通量的测量成为可能.     

痕量气体可调谐激光二极管吸收光谱分析系统在线自校准技术研究

可调谐激光二极管吸收光谱技术(TDLAS)是最有潜力的痕量气体在线监测技术之一。受测量原理的限制,其测量结果受温度和气压影响很大,目前多采用现场安装传感器来测量温度和气压信息,以对该误差进行修正。提出了利用在线参考气室对TDLAS系统中温度、气压变化引起的测量误差进行在线自校准;该参考气室内包含标准浓度的被测气体,并带有能变形的压力膜盒,工作的时候,该气室被放置在被测气体工作环境中,能自适应地调整室内气压和温度;在一次扫描过程中同时测得工作光路和参考光路的吸收光谱,并求得二者的吸收谱线强度比,即可得到校准后的被测痕量气体的浓度,无需考虑温度和气压影响;还介绍了这一自校准系统的原理、设计、实验和现场应用。     

Non-Voigt line-shape effects on retrievals of atmospheric ozone: Line-mixing effects

A theoretical approach is proposed to model line-mixing (LM) effects on absorption coefficients of O₃ perturbed by N₂ and air. It uses state-to-state rotational cross-sections calculated with a semi-classical approach and two empirical parameters, which enable switching from the state space to the line space. The first, associated with couplings within Q branches is deduced from a room temperature far-infrared spectrum. The second, governing line-couplings between R (or P) lines, is determined from a spectrum measured in the ν₁+ν₂+ν₃ band. The model developed is then successfully compared with measurements performed at room temperature for a relatively large range of pressure (0.7-8 atm) and in four different bands (from 3 to 300 μm). Accurate predictions are, in particular, obtained in the 10 μm (ν₁, ν₃) region, which is widely used for remote sensing purposes. Consequences of LM effects on retrievals of ozone atmospheric volume mixing ratios are then studied using simulated atmospheric spectra. The results show that LM leads to systematic spectra fit residuals and errors on the retrieved ozone amounts, which are small but might be detectable in measured atmospheric spectra.     

ALIS: An efficient method to compute high spectral resolution polarized solar radiances using the Monte Carlo approach

An efficient method to compute accurate polarized solar radiance spectra using the (3D) Monte Carlo model MYSTIC has been developed. Such high resolution spectra are measured by various satellite instruments for remote sensing of atmospheric trace gases. ALIS (Absorption Lines Importance Sampling) allows the calculation of spectra by tracing photons at only one wavelength. In order to take into account the spectral dependence of the absorption coefficient a spectral absorption weight is calculated for each photon path. At each scattering event the local estimate method is combined with an importance sampling method to take into account the spectral dependence of the scattering coefficient. Since each wavelength grid point is computed based on the same set of random photon paths, the statistical error is almost same for all wavelengths and hence the simulated spectrum is not noisy. The statistical error mainly results in a small relative deviation which is independent of wavelength and can be neglected for those remote sensing applications, where differential absorption features are of interest.Two example applications are presented: The simulation of shortwave-infrared polarized spectra as measured by GOSAT from which CO₂ is retrieved, and the simulation of the differential optical thickness in the visible spectral range which is derived from SCIAMACHY measurements to retrieve NO₂. The computational speed of ALIS (for 1D or 3D atmospheres) is of the order of or even faster than that of one-dimensional discrete ordinate methods, in particular when polarization is considered.     

Experimental intercomparison of the absorption cross-sections of nitrous acid (HONO) in the ultraviolet and mid-infrared spectral regions

Nitrous acid, HONO, is an important trace gas in tropospheric photochemistry, because it is a source of OH radicals. In order to obtain HONO concentrations from spectroscopic measurements, the knowledge of accurate absorption cross-sections is essential. Furthermore, the ultraviolet absorption cross-sections of HONO determine its atmospheric photolysis rates, which are still being debated. In particular, in a recent field study focusing on the photolysis frequency of HONO, the absolute values of the ultraviolet absorption cross-sections have been proposed as a potential source for systematic errors. For these reasons, we have compared the absorption cross-sections for HONO in the infrared (IR) and ultraviolet (UV) by performing simultaneous measurements in both spectral regions. Assuming that the IR cross-sections (that show good agreement between different studies) are correct, our study shows a good agreement between the consistent infrared studies and some selected accurate UV spectra published previously (about 6%) while a rather large disagreement (about 22%) is observed when using other UV data sets.     

基于可调谐激光吸收光谱技术的二硫化碳中红外光谱参数测量

采用4.6μm附近的量子级联激光器作为光源,搭建了一套二硫化碳(CS2)吸收光谱测量系统,结合可调谐二极管激光吸收光谱技术,对光谱范围为2178.99—2180.79 cm-1的CS2吸收光谱展开了深入研究,重点测量了2180.5—2180.74 cm~(-1)的四条吸收谱线,利用基于非线性最小二乘的多元线性回归算法对CS2吸收光谱进行拟合,精确得到了该范围内谱线的中心波长、线强以及空气展宽系数等光谱参数.经计算,对应谱线线强不确定度小于5%,空气展宽系数不确定度小于15%,这个结果可作为免标定CS2红外光谱探测的基础光谱参数,对痕量CS2气体传感具有重要意义.未来我们将进一步开展2170—2200 cm-1整个谱段的CS2谱线参数的测量,以期填补其在HITRAN和GEISA数据库光谱参数的空白.