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.     

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.     

Effects of vertical grid discretization in infrared transmission modeling

The vertical spacing of a discretization used to model transmission in the mid-infrared spectral range was investigated. The forward model employed in this study is a part of an algorithm used to retrieve trace gas profiles from high-resolution ground-based solar absorption Fourier transform infrared (FTIR) spectra, however, the results have general applicability. A finely spaced retrieval grid was constructed and made progressively more sparse in the troposphere and in the stratosphere. The effect was quantified in terms of transmission differences with respect to the most fine discretization for a suite of molecules (H₂O, O₃, CO, CO₂, CH₄, N₂O, NO, NO₂, HCl, HF, HNO₃, ClONO₂, and N₂) in microwindows commonly used in FTIR spectroscopy. Systematic differences in modeled transmissions are apparent when coarser grid schemes are used for all species and microwindows, though some are below random noise levels typical of spectra recorded at Toronto. The most significant are H₂O and O₃ at 0.30-0.73% and 0.10-0.34%, respectively. CO (0.13%), ClONO₂ (0.84%), and HF (1.03%) are also influenced by the interference of H₂O, which is sensitive to temperature interpolation errors via the lower state energy of the particular H₂O transition. O₃ is a significant interference in CO (0.42%) and ClONO₂ (0.31%) microwindows, but its influence is felt primarily via interpolation errors in the O₃ number concentration profile introduced by the coarser grids. HCl and HF themselves show the next most significant response in transmission to coarser stratospheric grids (∼0.18%). Finally, considering transmission differences >0.1% as significant in typical measurements, we identify maximum tropospheric and stratospheric layer widths that still lead to negligible transmission errors as, respectively, 0.6 and 2.0 km. These numbers can vary depending on the band or transition of interest, the signal-to-noise ratio of the measurement and the use of significantly different a priori volume mixing ratio profiles.     

The retrieval of profile and chemical information from ground-based UV-visible spectroscopic measurements

An algorithm has been developed to retrieve altitude information at different diurnal stages for trace gas species by combining direct-sun and zenith-sky UV-visible differential slant column density (DSCD) measurements. DSCDs are derived here using differential optical absorption spectroscopy. Combining the complementary zenith-sky measurements (sensitive to the stratosphere) with direct-sun measurements (sensitive to the troposphere) allows this vertical distinction. Trace gas species such as BrO and NO₂ have vertical profiles with strong diurnal dependence. Information about the diurnal variation is simultaneously retrieved with the altitude distribution of the trace gas. The retrieval is a formal optimal estimation profile retrieval, allowing a complete assessment of information content and errors.     

An improved high-resolution solar reference spectrum for earth's atmosphere measurements in the ultraviolet, visible, and near infrared

We have developed an improved solar reference spectrum for use in the analysis of atmospheric spectra from vacuum wavelengths of 200.07 through 1000.99 nm. The spectrum is developed by combining high spectral resolution ground-based and balloon-based solar measurements with lower spectral resolution but higher accuracy irradiance information. The new reference spectrum replaces our previous reference spectrum, and its derivatives, for use in a number of physical applications for analysis of atmospheric spectra, including: wavelength calibration; determination of instrument transfer (slit) functions; Ring effect (Raman scattering) correction; and correction for spectral undersampling of atmospheric spectra, particularly those that are dilute in absorbers. The applicability includes measurements from the GOME, SCIAMACHY, OMI, and OMPS satellite instruments as well as aircraft-, balloon-, and ground-based measurements.     

Evidence of reduced measurement uncertainties from an FTIR instrument intercomparison at Kiruna, Sweden

We report the results of an intercomparison of vertical column amounts of HCl, HF, N₂O, HNO₃, CH₄, O₃, CO₂ and N₂ derived from the spectra recorded by two ground-based FTIR spectrometers operated side-by-side using the sun as a source. The procedures used to record spectra and derive vertical column amounts followed the format of previous instrument intercomparisons organised by the Network for Detection of Stratospheric Change (NDSC), but the level of agreement achieved was significantly better than for previous intercomparisons.For most gases the differences were typically 1% or less, with at least one of the five datasets showing no statistically significant difference between the results from different instruments. Principal exceptions were HNO₃ and CO₂ when measured on the Mercury Cadmium Telluride (MCT) detectors. For these gases differences of between 2% and 3% were more typical. We present evidence that these larger differences are due to the effects of detector non-linearity and show that by applying an established non-linearity correction method the typical level of agreement can be improved to better than 1% for these gases.We suggest that the improved level of agreement achieved during this intercomparison is indicative of the current state of the art within the NDSC infra-red working group and is a result of improved understanding of the importance of critical alignment parameters and newly developed techniques to characterise the spectrometers’ performance.     

Multi-target retrieval (MTR): the simultaneous retrieval of pressure, temperature and volume mixing ratio profiles from limb-scanning atmospheric measurements

In this paper we describe a retrieval approach for the simultaneous determination of the altitude distributions of p, T and VMR of atmospheric constituents from limb-scanning measurements of the atmosphere. This analysis method, named multi-target retrieval (MTR), has been designed and implemented in a computer code aimed at the analysis of MIPAS-ENVISAT observations; however, the concepts implemented in MTR have a general validity and can be extended to the analysis of all type of limb-scanning observations. In order to assess performance and advantages of the proposed approach, MTR has been compared with the sequential analysis system implemented by ESA as the level-2 processor for MIPAS measurements. The comparison has been performed on a common set of target species and spectral intervals. The performed tests have shown that MTR produces results of better quality than a sequential retrieval. However, the simultaneous retrieval of p, T and water VMR has not lead to satisfactory results below the tropopause, because of the high correlation occurring between p and water VMR in the troposphere. We have shown that this problem can be fixed extending the MTR analysis to at least one further target whose spectral features decouple the retrieval of pressure and water VMR. Ozone was found to be a suitable target for this purpose. The advantages of the MTR analysis system in terms of systematic errors have also been discussed.     

地基消光测量确定大气气溶胶模型

 分别取大陆型、海洋型、城市型和Junge谱分布气溶胶模型,用6S辐射传输算法计算出对应于太阳光度计测量时的各波段大气气溶胶光学厚度。将模式计算值与测量值进行比较,确定测量地区的大气气溶胶模型。将该方法用于2004年在北京地区测量的太阳光度计数据,结果显示该地区当日实际大气在几种气溶胶模型中较为符合城市型气溶胶模型。     

Test of far-infrared atmospheric spectroscopy using wide-band balloon-borne measurements of the upwelling radiance

The spectroscopy of the constituents of the Earth's atmosphere that are active in the far infrared spectral region, among which the water vapour is the main one, has been validated through the analysis of wide-band nadir-looking spectra acquired with the Radiation Explorer in the Far Infrared—Prototype for Applications and Development (REFIR-PAD) Fourier transform spectroradiometer. The spectra, covering from 100 to with a unapodized resolution, were acquired during a balloon flight performed in a tropical region in 2005. Atmospheric variables, namely water vapour and temperature vertical profiles, were retrieved from the REFIR-PAD data, and the residuals of the fitting are here critically analysed for the search of systematic effects that can be ascribed to spectroscopic errors. In the spectral interval between 150 and nosignificant inconsistency is detected between the residuals and the measurement uncertainty, proving the good quality of the radiative transfer model and of the HITRAN 2004 spectroscopic database. Significant difference are instead observed when the HITRAN 2000 database is used.     

Analysis of the FTIR spectrum of pyrazine using evolutionary algorithms

The FTIR spectrum of pyrazine in the gas phase has been measured and analyzed using automated evolutionary algorithms. For the stronger bands, the rotational constants for ground and vibrationally excited states, the correct band types and in some cases centrifugal distortion constants could be extracted. Several hot hands have been identified and assigned by comparison to a cubic force field calculation at the MP2/6-311G(d,p) level of theory. Vibrationally averaged rotational constants for the excited bands can give a further guidance in the assignment of the vibrational bands.     

Improvements for ground-based remote sensing of atmospheric aerosol properties by additional polarimetric measurements

We discuss the improvements in the aerosol properties characterization resulting from the additional multi-wavelength polarization measurements measured by a new CIMEL polarized sun/sky-photometer, CE318-DP. In order to process direct-sun, sky and polarization measurements in a wide spectral range (340–1640 nm), we developed new calibration methods and strategies, e.g. using the Langley plot method to calibrate both direct-sun irradiance and sky radiance, as well as combining laboratory facilities with a vicarious method to calibrate the polarized sky measurements. For studying the impact of new polarimetric measurements on the retrievals of aerosol properties, we have processed an extensive record of field measurements using an updated Dubovik and King retrieval algorithm [Dubovik O, Sinyuk A, Lapyonok T, Holben BN, Mishchenko MI, et al. Application of spheroid models to account for aerosol particle nonsphericity in remote sensing of desert dust. J Geophys Res 2006;111:D11208.]. A preliminary analysis shows that adding polarization in the inversion can reduce possible errors (notably for about 30% of our field cases) in the fine mode size distribution, real part of refractive index and particle shape parameter retrievals, especially for small particles.     

Fast approximate technique for the cumulative wavenumber model to modeling radiative transfer in a mixture of real gas media

In the cumulative wavenumber (CW) model, the total range of the absorption cross-section Cη is subdivided into the supplementary absorption cross-section of gray gases C_j, j=1,…,n, where n is the number of gray gases; and the wavenumber region is subdivided into intervals Δ_i=[η_i−1, η_i], i=1, 2,…,p, where p is the number of intervals. The intersection of the two spectral subdivisions is used to define the modeling of the fractional gray gas D_ij. In the CW model, we solve the radiative transfer equation (RTE) in every subinterval D_ij; then it is necessary to solve n x p times the spectral form of the RTE for complete spectral integration. In this work, the CW model is used with a numerical approximation technique based on additive properties of radiative intensity to reduce the solution of RTE to n new fractional gray gas D_j for complete spectral integration. The CW model was first coupled with the discrete ordinates method and the accuracy of the simplified technique and the algorithm was first examined for one-dimensional homogeneous media; results are compared with line-by-line calculations and it is found that the CW model with the simplified technique is exact for the homogeneous media examined. Also, the fast approach is tested in the diffuse reflecting boundaries case. The CW model is implemented in a bi-dimensional enclosure containing real gases in isothermal cases. Afterwards, this approximate technique is extended to non-isothermal and non-homogeneous cases; the results are compared with line-by-line calculations taken from literature and good agreement was found. The results obtained using the acceleration technique for the CW model agree with the results of original CW model. With this acceleration technique the CPU time decreases p times. Spectral database HITRAN and HITEMP are used to obtain the molecular absorption spectrum of the gases.     

Operational retrieval algorithms for JEM/SMILES level 2 data processing system

To measure the thermal emission from stratospheric minor species with high sensitivity, the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES) aboard the Japanese Experiment Module (JEM) of the International Space Station (ISS) carries 4 K cooled Superconductor–Insulator–Superconductor (SIS) mixers. The major feature of the SMILES is its high-sensitive measurement ability with low system noise temperature less than 700 K.As a part of the ground system for the SMILES, a level 2 data processing system (DPS-L2) has been developed. It retrieves the density distributions of the target species from calibrated spectra in near-real-time. The retrieval process consists of two parts: the forward model, which computes radiative transfer, and the inverse model, which deduces atmospheric states. Since the forward model must provide the most accurate basis for results and be implemented under limited computing resources, the forward model algorithm for an operational system has to be accurate and fast. Hence, the algorithm is improved (1) by designing accurate instrument functions such as the instrumental field of view (FOV), sideband rejection ratio of sideband separator, and spectral responses of acousto-optic spectrometer (AOS) and (2) by optimizing radiative transfer calculation.This paper presents the development of the DPS-L2 along with the details on its algorithm and the algorithm performance. The accuracy of this algorithm is better than 1%, and the processing time for single-scan spectra is less than 1 min with eight parallel processings using a 3.16-GHz Quad-Core Intel Xeon processor. Thus, this algorithm is suitable for the SMILES measurement.     

On the retrieval of ice cloud particle shapes from POLDER measurements

Shapes of ice crystals can significantly affect the radiative transfer in ice clouds. The angular distribution of the polarized reflectance over ice clouds strongly depends on ice crystal shapes. Although the angular-distribution features of the total or polarized reflectance over ice clouds imply a possibility of retrieving ice cloud particle shapes by use of remote sensing data, the accuracy of the retrieval must be evaluated. In this study, a technique that applies single ice crystal habit and multidirectional polarized radiance to retrieve ice cloud particle shapes is assessed. Our sensitivity studies show that the retrieved particle shapes from this algorithm can be considered good approximations to those in actual clouds in calculation of the phase matrix elements. However, this algorithm can only work well under the following conditions: (1) the retrievable must be overcast and thick ice cloud pixels, (2) the particles in the cloud must be randomly oriented, (3) the particle shapes and size distributions used in the lookup tables must be representative, and (4) the multi-angle polarized measurements must be accurate and sufficient to identify ice cloud pixels of randomly oriented particles. In practice, these conditions will exclude most of the measured cloud pixels. Additionally, because the polarized measurements are only sensitive to the upper cloud part not deeper than an optical thickness of 4, the retrieved particle shapes with the polarized radiance may only approximate those in the upper parts of the clouds. In other words, for thicker clouds with vertical inhomogeneity in particle shapes, these retrieved particle shapes cannot represent those of whole clouds. More robust algorithm is needed in accurate retrieval of ice cloud particle shapes.     

MARC: A code for the retrieval of atmospheric parameters from millimeter-wave limb measurements

A new data analysis software is presented that has been developed for the retrieval of atmospheric minor constituents from limb-sounding observations made in the millimeter and sub-millimeter spectral regions. The code, which is called MARC (Millimetre-wave Atmospheric-Retrieval Code), has been designed to analyze the observations of the MARSCHALS (Millimetre-wave Airborne Receivers for Spectroscopic CHaracterisation in Atmospheric Limb-Sounding) instrument which operates on the M-55 stratospheric aircraft. The main objective of the analysis of MARSCHALS observations will be to assess long-wave measurement capabilities for the study of the upper troposphere and lower stratosphere regions. The key questions will be the accuracy and spatial resolution that can be achieved by long-wave measurements in presence of clouds and horizontal gradients.MARC performs a global-fit multi-target retrieval, in which optimal estimation is used and errors of the forward model parameters are taken into account for the definition of the cost function minimized in the retrieval. With these features it is easy to use the variables of the problem as either forward model constant parameters or retrieved unknowns with minimum impact on the stability of the retrieval. MARC can perform a wide spectral-band analysis of the observations without a selection of the analyzed channels, and the retrieval process provides an error budget of the retrieved unknowns that includes both the forward model errors and the measurement errors. The error budget obtained in this way is smaller than that obtained when accounting a posteriori for the systematic errors. The new combination of the retrieval features makes possible an efficient and optimal exploitation of the information content of the observations.     

超光谱红外卫星资料同步反演不同地表类型的大气廓线、地表温度和地表发射率

大气温度、水汽、地表温度和地表发射率是大气和地表的本征信息量。利用卫星红外资料精确反演大气温湿廓线有利于准确预报天气和研究气候变化,同时地表温度和地表发射率光谱的反演为研究植物生长与作物产量、地表水分蒸发与循环、能量平衡、地表成分及物理性质、气候变迁与全球环境提供重要参数指标。把大气和地面作为一个整体系统来考虑,建立一种能同步反演大气温度廓线、大气水汽廓线、地表温度和地表发射率的反演方法,利用超光谱红外卫星资料(atmospheric infrared sounder, AIRS),针对我国新疆地区沙漠和雪地两种典型发射率地表同步反演大气温度廓线、水汽廓线、地表温度和地表发射率。反演方法首先线性化地球-大气系统红外辐射传输方程, 提出通过经验正交函数构建大气廓线和地表发射率光谱,有效减少反演变量数,建立同步物理反演模式,然后以美国国家环境预报中心(National Centers for Environmental Prediction,NCEP)的预报结果(初始大气温度、水汽廓线以及地表参数)作为初始值,最后通过牛顿迭代得到最优化解。反演观测区域覆盖我国新疆塔克拉玛干沙漠和准噶尔盆地,分别选择位于塔克拉玛干沙漠腹地的塔中探测站(纬度38.98°, 经度83.64°)和准噶尔盆地的阜康荒漠生态系统国家野外科学观测研究站(纬度44.2°, 经度87.9° )为反演地面验证点。反演结果表明,塔克拉玛干沙漠地表温度明显高于准噶尔盆地地表温度,与实际情况相一致;根据反演的8.6和13.4 μm处的地表发射率分布情况,可以看出在8.6 μm处沙漠地表发射率明显低于雪地发射率,在6～15 μm范围内,反演的沙漠地区(塔中站)地表发射率和雪地地区(阜康站)地表发射率与美国喷气推进实验室测量的沙漠发射率光谱和雪地发射率光谱相一致。研究表明,把大气和地面作为一个整体系统来考虑,把地表发射率加入到反演中,通过比较和分析沙漠地区(塔中)和雪地地区(阜康)的大气廓线反演结果与当地气象探空值和传统反演方法反演值,改进了大气温度廓线和水汽廓线反演精度,特别是边界层温度和水汽改进尤为明显;同时分析表明在发射率光谱变化较大的沙漠地区, 大气廓线反演精度的改进比雪地要高,这是由于地表发射率光谱在沙漠、戈壁地区变化较大,而雪地的发射率光谱变化不大。用该方法针对地表发射率光谱变化较大的地区(沙漠)同步反演大气廓线、地表温度和地表发射率,可以更有效的提高大气温度廓线、水汽廓线的反演精度。该研究结果可以为数值天气预报和我国未来超光谱红外卫星应用提供服务和有力支持, 具有十分重要的意义。     

Multi-decade measurements of the long-term trends of atmospheric species by high-spectral-resolution infrared solar absorption spectroscopy

Solar absorption spectra were recorded for the first time in 5 years with the McMath Fourier transform spectrometer at the US National Solar Observatory on Kitt Peak in southern Arizona, USA (31.91°N latitude, 111.61°W longitude, 2.09 km altitude). The solar absorption spectra cover 750-1300 and 1850-5000 cm⁻¹ and were recorded on 20 days during March-June 2009. The measurements mark the continuation of a long-term record of atmospheric chemical composition measurements that have been used to quantify seasonal cycles and long-term trends of both tropospheric and stratospheric species from observations that began in 1977. Fits to the measured spectra have been performed, and they indicate the spectra obtained since return to operational status are nearly free of channeling and the instrument line shape function is well reproduced taking into account the measurement parameters. We report updated time series measurements of total columns for six atmospheric species and their analysis for seasonal cycles and long-term trends. As an example, the time series fit shows a decrease in the annual increase rate in Montreal-Protocol-regulated chlorofluorocarbon CCl₂F₂ from 1.51±0.38% yr⁻¹ at the beginning of the time span to −1.54±1.28% yr⁻¹ at the end of the time span, 1 sigma, and hence provides evidence for the impact of those regulations on the trend.