Remote sensing by open-path FTIR spectroscopy. Comparison of different analysis techniques applied to ozone and carbon monoxide detection

The analysis of FTIR spectra is usually carried out by commercial programs that use methods based on classical least-squares (CLS) procedures These procedures are normally appropriate to analyse O-P FTIR spectra, but some occasional discrepancies with standard extractive methods have been observed.In this work, a line-by-line method (SFIT) is additionally used. Our purpose is to explain the sporadic discrepancies observed between CLS and standard extractive method results and to study the capability of both methods (CLS and SFIT) to analyse open-path measurements. This capability has been studied for ozone and carbon monoxide.It has been demonstrated that in CLS-based methods discrepancies are induced by the experimental background reference spectrum. In these cases, SFIT results are in very good agreement with the standard extractive methods.     

Analysis of atmospheric infrared spectra for altitude distribution of atmospheric trace constituents—I. Method of analysis

A line-by-line, layer-by-layer method is described for the analysis of infrared atmospheric spectra in terms of atmospheric trace constituents. The method covers spectra obtained at both small and large zenith angles. For the latter, a detailed consideration of the air mass along the ray is discussed.     

Line narrowing effect on the retrieval of HF and HCl vertical profiles from ground-based FTIR measurements

Collision-induced line narrowing, which has been discovered in the 1950s and investigated thoroughly in the laboratory since then, has yet never been taken into account in the spectroscopic remote sensing of the atmosphere. This work investigates the effect of collision-induced line narrowing onto the retrieval of HCl and HF vertical profiles from ground-based solar absorption FTIR measurements made at the NDSC station of the Jungfraujoch (46.5^°N, 8^°E and 3580 m above see level). The retrievals are performed with the Atmosphit software, recently developed at the Université Libre de Bruxelles. It is presented in this paper for the first time and is validated against the widely used SFIT2 software. The impact of the line narrowing onto the retrieval of HCl and HF vertical profiles is examined relying on careful information content and error budget analyses. We report that the effect is relatively weak for HCl but significant for HF. Confirmation of the need to take the line narrowing into account for the retrieval of vertical profiles from ground-based FTIR spectra is given by comparison with data from the HALOE space borne instrument, rather insensitive to this spectroscopic effect.     

Spectral line finding program for atmospheric remote sensing using full radiation transfer

We have developed a line-by-line code to simulate atmospheric spectra in the infrared spectral region assuming a remote light source of selectable temperature. Selecting the source temperature allows simulation of, for example, solar absorption spectra, lunar absorption spectra or emission spectra. The code is applicable for different geometries, from the ground, balloon or from satellite, and allows a simple search for the most suitable lines for the retrieval of atmospheric trace gas concentrations for the different geometries. In addition, a first estimate of the optimized microwindow size and the most important interfering gases that need to be considered is calculated automatically. This approach is of importance in cases where it is necessary to analyze numerous lines simultaneously to get sufficient precision in the trace gas concentration retrievals. Examples for H₂O and CO are given.     

多波段激光雷达颗粒物质量浓度探测方法

为了获得大气颗粒物的质量浓度廓线,提出一种基于多波段激光雷达回波信号的大气气溶胶消光系数与颗粒物质量消光效率相结合的新型算法。该方法利用覆盖紫外到近红外波段的激光雷达作为遥感探测工具,获取气溶胶的消光与后向散射系数,反演得到气溶胶粒子谱分布;同时,根据米散射理论算出气溶胶消光效率,结合粒子谱分布,提出颗粒物质量消光效率模型,从而建立基于消光系数与质量消光效率相结合的反演颗粒物质量浓度的新型数学模型与算法。采用该算法对两组不同天气条件多波段激光雷达实测数据进行反演,并与地表采用的颗粒物浓度对比,证明该方法的可行性,为实现颗粒物质量浓度空间分布的探测提供科学依据和方法论。     

基于光线追迹法的球形大粒子的多次散射计算

基于光线追迹法模拟了球形大粒子的多次散射过程,利用菲涅耳公式建立了散射矩阵的理论表达式,并利用Matlab对计算过程进行编程。以水滴为例进行了定量计算,获得了散射功率随散射次数和散射角的分布。相关结论可用于光学大气传输的定量计算。     

Intercomparison of retrieval codes used for the analysis of high-resolution, ground-based FTIR measurements

A rigorous and systematic intercomparison of codes used for the retrieval of trace gas profiles from high-resolution ground-based solar absorption FTIR measurements is presented for the first time. Spectra were analyzed with the two widely used independent, retrieval codes: SFIT2 and PROFFIT9. Vertical profiles of O₃, HNO₃, HDO, and N₂O were derived from the same set of typical observed spectra. Analysis of O₃ was improved by using updated line parameters. It is shown that profiles and total column amounts are in excellent agreement, when similar constraints are applied, and that the resolution kernel matrices are also consistent. Owing to the limited altitude resolution of ground-based observations, the impact of the constraints on the solution is not negligible. It is shown that the results are also compatible for independently chosen constraints. Perspectives for refined constraints are discussed. It can be concluded that the error budget introduced by the radiative transfer code and the retrieval algorithm on total columns deduced from high-resolution ground-based solar FTIR spectra is below 1%.     

激光诱导击穿空气等离子体时间分辨特性的光谱研究

空气等离子体的时间行为对空气环境下激光诱导等离子体形成过程的研究有重要意义.本文将纳秒Nd:YAG脉冲激光(1064 nm)聚焦于一个大气压的空气中,诱导其产生等离子体.利用具有纳秒时间分辨功能的PI-MAX-II型ICCD,采用时间分辨光谱方法,研究了大气环境下激光诱导等离子体的时间行为.大气环境下的激光诱导等离子体光谱广泛分布于300—900 nm范围内,并且是由带状光谱和线状光谱叠加而成的.根据美国国家标准与技术研究院原子发射谱线数据库,对等离子体光谱中的氧、氮、氢等元素的特征谱线进行了识别和归属.给出了激光诱导击穿大气等离子体光谱随时间演化的直观图像,根据空气等离子体发射谱线计算了等离子体电子温度和等离子体电子密度.这些结果对于提高在大气环境下进行的在线测量结果的准确性和精确性具有重要的科学意义.     

Spectra—A model for K-shell spectroscopy

X-ray spectroscopy is a powerful tool for understanding the kinetics of highly ionized plasmas. Its usefulness depends on the accuracy of the model used in analyzing spectra. We have developed a computer code for modeling and analyzing plasmas which is highly accurate as well as fast and easy to use. It produces synthetic spectra for hydrogen-like and helium-like ions at arbitrary density and temperature. Populations are calculated from rate equations including all relevant collisional and radiative process. The level populations of the hydrogen, helium and lithium-like ionization stages are calculated explicitly; those of all other ionization stages are lumped into one level. The microfield distribution and the shape of the line profiles are determined using detailed calculations. The code includes graphics to plot line ratios and synthetic spectra, and to do on-line analysis of experiments. The usefulness of this technique is demonstrated by analyzing the spectra from three different experiments: a laser irradiated aluminum disk; a neon gas puff pinch; and a laser imploded gas microballon.     

Path-length distribution of ions reflected from a solid: Theory and computer simulation

Theoretical methods and Monte Carlo procedure are used to study path-length distributions of ions reflected from a solid. The theoretical analysis is based on the solution of the integral Chandrasekhar equation for the Laplace transform of the distribution function. A family of curves is obtained for path-length distributions at several ion energies and mass ratios of ions and target atoms. A computer code for simulation is based on the approximation of pair collisions and a gas model of solid. The simulated results are compared with the theoretical results and published data.     

Continuous field measurements of delta(13)C-CO(2) and trace gases by FTIR spectroscopy

Continuous analysis of the (13)C/(12)C ratio of atmospheric CO(2) (delta(13)C-CO(2)) is a powerful tool to quantify CO(2) flux strengths of the two major ecosystem processes assimilation and respiration. Traditional laboratory techniques such as isotope ratio mass spectrometry (IRMS) in combination with flask sampling are subject to technical limitations that do not allow to fully characterising variations of atmospheric delta(13)C-CO(2) at all relevant timescales. In our study, we demonstrate the strength of Fourier transform infrared (FTIR) spectroscopy in combination with a PLS-based calibration strategy for online analysis of delta(13)C-CO(2) in ambient air. The ability of the instrument to measure delta(13)C-CO(2) was tested on a grassland field-site and compared with standard laboratory-based IRMS measurements made on field-collected flask samples. Both methods were in excellent agreement, with an average difference of 0.4 per thousand (n=81). Simultaneously, other important trace gases such as CO, N(2)O and CH(4) were analysed by FTIR spectroscopy.     

一种半球形天空亮度测量仪器的研制

在大气光学领域中,天空亮度分布有着重要的应用.简要介绍了天空亮度的测量原理,在分析同类测量仪器的基础上,提出了一种用于白天的,可见及近红外波段天空亮度测量仪器的设计,介绍了系统的组成和探测器的选择.经过定标,仪器能够得到天空亮度的绝对值,其结果反映了真实天空亮度分布的变化.该仪器弥补了传统的天空亮度测量仪器住测量波段、实时性、便携性等方面的不足,更好地满足了实际的科研需求.     

Application of Origen2.1 in the decay photon spectrum calculation of spallation products

Origen2.1 is a widely used computer code for calculating the burnup, decay, and processing of radioactive materials. However, the nuclide library of Origen2.1 is used for existing reactors like pressurized water reactors. To calculate the photon spectrum released by the decay of spallation products, we have made specific libraries for the ADS tungsten spallation target, based on the results given by the FLUKA Monte Carlo code. All the data used to make the Origen2.1 libraries are obtained from Nuclear structure & decay Data (NuDat2.6). The accumulated activity of spallation products and the contribution of nuclides to photon emission are given in this paper.     

Real-time field measurements of stable isotopes in water and CO2 by Fourier transform infrared spectrometry

Continuous records of isotope behaviour in the environment are invaluable to understanding mass and energy fluxes. Although techniques such as isotope ratio mass spectrometry provide high precision data, they are not well suited to the analysis of a large number of samples and are currently restricted to use in the laboratory. Fourier transform infrared spectrometers are relatively cheap and sufficiently portable and robust to be taken into the field to collect continuous records of gas-phase isotope behaviour. Several examples of the application of this technique will be presented. One data set provides half-hourly determinations of vertical profiles of D/H in water vapour above agricultural fields over a 3-week period; the same infrared spectra can also be used to determine 13C/12C in CO2. The technique has also been applied to the study of CO2 in ambient air and in a limestone cave system. Some of the features and complications associated with the method will also be considered.     

Ozone profiles and total column amounts derived at Izaña, Tenerife Island, from FTIR solar absorption spectra, and its validation by an intercomparison to ECC-sonde and Brewer spectrometer measurements

Since February 1999 high-resolution Fourier transform infrared (FTIR) solar absorption spectra are recorded at the Izaña Observatory (, 2370 m a.s.l.), which forms part of the network for detection of stratospheric change (NDSC). The vertical distribution of the ozone amount was deduced from the spectra by using the retrieval code PROFFIT. Two microwindows at 782.5 and are used whereby an individually and regularly determined instrumental line shape (ILS) was applied. A detailed error analysis of the ozone retrieval is performed, i.e. the height-dependent impact of all important error sources on the retrieved profiles is estimated. The retrieved total column amounts and profiles as well as their estimated error budgets are verified by comparisons with column amounts and profiles derived from Brewer spectrometer and ECC-sonde measurements performed simultaneously at the same location. Whereas the mean difference of 1.9% of the FTIR total column amounts and the Brewer data lies within the precision of the instruments, systematic differences of up to 9% between FTIR and ECC-sonde profile are observed above . The assumed precisions of the experiments are consistent with the experimental results, which demonstrates the excellent characterization of the FTIR data. The analysis of systematic errors allows to conclude that the systematic differences are mainly due to the sonde data since the systematic errors in the FTIR profile can only explain a small part of them.     

Measurements of atmospheric antiprotons

We measured atmospheric antiproton spectra in the energy range 0.2 to 3.4 GeV, at sea level and at balloon altitude in the atmospheric depth range 4.5 to 26 g/cm². The observed energy spectra, including our previous measurements at mountain altitude, were compared with estimated spectra calculated on various assumptions regarding the energy distribution of antiprotons that interacted with air nuclei.     

FTIR直接测定法在解决忍冬科一些分类学问题中的应用研究

应用傅里叶变换红外光谱 (FTIR) 法测定了忍冬科5属12种植物的红外光谱,对其红外光谱及系统关系进行了分析。结果表明：各分类群的红外光谱具有高度特异性和重现性,七子花属与忍冬族和北极花族的关系都比较接近,表明七子花属有可能在一定程度上联系着忍冬族和北极花族,而接骨木属和荚蒾属与科内其他属的距离并不远,支持目前把这两属归入忍冬科的分类方法。说明利用已知的标准红外光谱图库,可以鉴定和区分出这些属或其他属植物的种类及关系。     

A unified model of preequilibrium decay

A microscopic exciton model has been developed which describes the time evolution of a highly excited nucleus through a series of binary collisions creating additional particle-hole pairs. Starting from an arbitrary exciton density distribution, the spectral shapes of the succeeding stages are generated through recursion relations which keep track of the “exciton flux” explicitely. The computer code BEEFALO provides particle spectra and average life times of the successive stages. The results are compared with the predictions of other preequilibrium models using “equal probability” density distributions. The controversy about the use of single particle orn-exciton state life times has been resolved by showing that both approaches lead to the same particle spectra if proper book-keeping is made through appropriate recursion relations.     

Gas Chromatography-Fourier Transform Infrared Spectrometry

Abstract

Difficult mixture analysis problems can usually be simplified when chromatographic separating techniques are employed to isolate individual mixture components. Many different discrimination methods based on observation of physical or chemical properties have been developed to detect substances Separated by gas chromatography. These detectors facilitate quantitative analysis when mixture component identities are known but provide little structural information for identification of unknown mixture components. On the other hand, mass spectrometry and infrared spectroscopy can provide a wealth of structural information. Mass spectra and infrared spectra are representative of eluent structure in a complementary manner. Mass spectrometry is often used to obtain molecular weight information and can be used to distinguish homologues. Infrared spectra reveal molecular functionalities and are particularly useful for isomer discrimination.     

常压射流等离子体发射光谱研究

使用改进介质阻挡放电装置生成常压射流等离子体,采用光纤光栅光谱仪在300～1 000 nm范围记录了不同放电电压的氩气发射光谱,并比较了空气和氩气常压介质阻挡放电等离子体发射光谱,分析发现氩气发射光谱中的谱线都是氩原子的发射谱线,表明常压射流装置产生的等离子体全部为氩等离子体,而无其他空气成分参与放电。为测量电子激发温度,选用相距较近的763.51和772.42 nm两条光谱线对电子温度进行分析,结果表明电子激发温度的范围在0.1～0.3 eV,而且它还随着放电电压的增加而增加。初步使用“红外测温仪”测量被处理材料表面温度,结果发现材料表面的温度也随着放电电压的增加而增加,范围在50～100 ℃,材料表面温度的变化趋势可以近似表征等离子体宏观温度变化趋势。通过分析常压射流等离子体的温度特性,探讨了常压射流等离子体温度对材料改性研究的意义。