机载成像差分吸收光谱技术测量区域NO2二维分布研究

本文主要介绍了一种快速测量区域大气痕量气体二维分布的方法——机载成像差分吸收光谱(differential optical absorption spectroscopy, DOAS)技术. 该技术基于成像光谱仪, 利用DOAS算法, 对痕量气体大范围分布快速扫描成像, 可实现污染源扩散趋势的可视化观测, 应用于污染源定位、污染源排放率监测、污染物传输演化等研究. 文中详细介绍了研制的机载成像DOAS系统, 并利用该系统开展飞行实验, 快速获取了飞行轨迹上空的NO₂浓度分布. 实验中针对重点关注区域进行扫描测量, 成功获取了高分辨率的NO₂二维分布图, 分析了污染扩散趋势, 并结合风场数据, 估算污染点源的NO₂排放率为1570 kg/h.     

不同温度压力对浓度反演精度的定量分析

自研傅里叶变换红外光谱仪在龙凤山大气本底站测量CO₂,CH₄等温室气体.自研仪器的测量结果与符合世界气象组织标准的本底站仪器的测量结果进行对比,结果表明:自研仪器与本底站仪器测量的CO₂浓度值相关系数为0.9576,均方根误差为18.6015.自研仪器使用标准温度、压力下的校准光谱反演浓度,但测量气体的温度随着气温变化,导致自研仪器反演浓度有误差.基于以上分析,提取高分辨率透射分子吸收数据库参数计算吸收截面并结合仪器线形计算不同温度、压力下的校准光谱,根据不同温度、压力下的校准光谱来校准反演浓度.校准后,自研与本底站仪器测量的CO₂浓度值相关系数为0.9637,均方根误差为6.7800.自研与本底站仪器测量的CO₂浓度值相关系数提高,绝对误差减小,说明校准算法提高了测量结果的精确度.     

基于激光诱导水拉曼抑制法的油膜厚度测量方法研究

为了实现水体表面油膜厚度的快速测量分析,以266 nm的激光作为探测系统的激发光源,基于激光诱导水拉曼散射光谱检测技术,通过获取不同种类不同厚度油膜存在下水拉曼光谱信息,建立油膜厚度反演模型。采用高斯函数拟合法校正了荧光光谱对拉曼光谱的干扰。然后根据水拉曼抑制法结合非线性最小二乘优化算法,建立油膜厚度反演模型。结果表明：对92#汽油、0#柴油、美孚机油20w-40、壳牌润滑油10w-40、采埃孚变速箱油AG6和原油油膜能探测到的油膜厚度范围为0.19~379.22 μm。采用水拉曼光谱-油膜厚度反演模型预测油膜厚度的平均相对误差在8.14%~15.81%之间。该方法能实现实验室条件下对微米级油膜的测量。     

Electronic excitations by chemical reactions on metal surfaces

Dissipation of chemical energy released in exothermic reactions at metal surfaces may happen adiabatically by creation of phonons or non-adiabatically by excitation of the electronic system of the metal or the reactants. In the past decades, the only direct experimental evidence for such non-adiabatic reactions has been exoelectron emission into vacuum and surface chemiluminescence which are observed in a special class of very exothermic reactions. The creation of e–h pairs in the metal has been discussed in many theoretical models but it was only recently that a novel experimental approach using Schottky diodes with ultrathin metal films makes direct measurement of reaction-induced hot electrons and holes possible. The chemical reaction creates hot charge carriers which travel ballistically from the metal film surface toward the Schottky interface and are detected as a chemicurrent in the diode. By now, such currents have been observed during adsorption of atomic hydrogen and deuterium on Ag, Cu and Fe surfaces as well as chemisorption of atomic and molecular oxygen, of NO and NO₂ molecules and of certain hydrocarbons on Ag. This paper reviews briefly exoelectron and chemiluminescence experiments and the concept of the Nørskov–Newns–Lundqvist model. The major part is devoted to the detection of chemically induced e–h pairs with thin metal film Si Schottky diodes by discussing the different influences on the chemicurrent magnitude and presenting experimental results predominantly with hydrogen and deuterium atoms. The experiments introduce a new method to investigate surface reaction kinetics and dynamics by use of an electronic device. In addition, the diodes may be used as selective reactive gas sensors.     

LIBS技术在污染土壤重金属含量分布测量中的应用

诱导击穿光谱技术(LIBS)具有实时快速、多元素同时探测的优势,并且无需样品预处理,检测成本低,是土壤重金属定量分析检测的一种重要分析手段。将LIBS技术应用于冶炼厂区周围土壤中重金属的含量分布分析研究,利用Cu,Pb和Cr三种元素的特征谱线强度分析了冶炼厂区周围土壤中Cu,Pb和Cr三种元素的含量分布。实验结果表明冶炼厂区土壤LIBS光谱中Cu和Pb两种元素的特征谱线强度分布与实际含量分布呈较好的线性关系,而Cr元素的特征谱线强度分布与实际含量分布相关性较差。为了提高Cr元素含量分布分析的准确性,利用CF-LIBS结合Saha方程应用于土壤Cr元素的含量分布分析中。实验结果表明基于CF-LIBS计算的Cr和Si两种元素含量比值分布与土壤Cr元素的实际含量分布之间具有良好的一致性。相比于其他的化学分析方法,LIBS技术结合CF-LIBS可以快速的对区域土壤重金属元素的含量分布进行检测,因此将LIBS技术与CF-LIBS相结合用于土壤重金属的含量分布检测中,为污染区域的重金属防治提供方向。     

基于太阳吸收光谱观测大气一氧化碳柱总量

基于地基高分辨率傅里叶变换红外光谱技术观测合肥地区一氧化碳(CO)垂直柱总量的变化,连续采集近红外太阳吸收光谱,获得2015年9月至2016年7月整层大气CO的垂直柱总量的时间序列。观测结果显示合肥地区大气中柱平均干空气混合比(XCO)有着明显的季节变化,在2015年10月有着较小值,然后逐渐增加,到2016年3月达到最大值,之后逐渐下降,在2016年7月底达到最小值,并分析了季节变化的原因。为了对地基近红外波段观测进行验证,采用MOPITT卫星数据和站点同一光谱仪采集的中红外光谱反演的CO柱总量与同期测量的数据进行比对。结果表明,MOPITT卫星数据与地基观测值的季节变化一致,而MOPITT观测值整体高于地基FTS观测值;近红外和中红外波段反演的CO柱总量季节变化范围一致。将地基观测和卫星观测数据进行日平均计算, 并进行相关性分析,得到的地基近红外和卫星观测、地基中红外的CO日平均柱总量的线型回归相关系数分别为0.85和0.91,显示出高的相关性,证明了地基近红外波段反演CO垂直柱总量数据的准确性。首次采用地基高分辨率傅里叶变换红外光谱技术观测合肥地区CO的垂直柱总量,并将得到的观测结果与卫星数据比对,得到准确的CO的垂直柱总量,为解大气CO的时空分布状况及其演变规律、追踪合肥地区CO的源汇分布提供理论依据。     

宽带腔增强吸收光谱法测量大气NO2定标方法研究

非相干宽带腔增强吸收光谱法定量探测大气痕量气体浓度需要准确定标。以定量探测大气NO₂为目的,建立了基于蓝色发光二极管光源的非相干宽带腔增强吸收光谱测量系统,研究了(1)仅使用浓度已知的NO₂吸收光谱、(2)同时使用浓度已知的NO₂和纯氧气中氧气二聚体O₂-O₂吸收光谱、(3)利用纯氮气和纯氦气的瑞利散射消光差异等三种方法,分别获取非相干宽带腔增强吸收光谱在430～490 nm波段的镜片反射率定标曲线。三种方法得到的镜片反射率最大值对应波长均约为460 nm,但这些最大值存在一定差异,分别为0.999 25,0.999 33和0.999 37。利用NO₂样气吸收测量对比了三种定标方法,发现方法(1)与另外两种方法的测量结果不一致性分别约为14%和19%,而后两种方法所测结果的不一致性仅为4%。测量结果表明,NO₂标准气体浓度的不准确性以及壁损耗等因素恶化了方法(1)的定标精度,应尽量避免使用该定标方法。通过对实际大气中NO₂和O₂-O₂在440～485 nm波段内的同时测量,进一步验证了非相干宽带腔增强吸收光谱法的高灵敏度以及所用标定方法的有效性。     

Laser-enhanced negative ion mass spectroscopy for weakly electron-attaching species

We report the first observation of efficient negative ion formation in excimer-laser irradiated benzene and toluene. These negative ions were formed via enhanced electron attachment to highly-excited states produced by the laser radiation. The potential of this technique as an analytical tool is discussed. Due to the general nature of the enhanced electron attachment mechanism involved, this technique can be expected to be applicable for a wide variety of molecules.     

Determination of heavy metals by inductively coupled plasma mass spectrometry after on-line separation and preconcentration

A method for the determination of Cu, As, Se, Cd, In, Hg, Tl, Pb and Bi in waters and in biological materials by inductively coupled plasma mass spectrometry, after an on-line separation, is described. The matrix separation and analyte preconcentration is accomplished by retention of the analytes complexed with the ammonium salt of O,O-diethyl dithiophosphoric acid in a HNO₃ solution on C₁₈ immobilized on silica in a minicolumn. Methanol, as eluent, is introduced in the conventional pneumatic nebulizer of the instrument. In order to use the best compromise conditions, concerning the ligand and acid concentrations, the analytes were determined in two separate groups. The enrichment factors were in the range from 5 to 61, depending on the analyte. The limits of detection varied from 0.43 ng L⁻¹ for Bi to 33 ng L⁻¹ for Cu. The sample consumption is only 2.3 mL for each group and the sampling frequency is 21 h⁻¹. The accuracy was tested by analysing five certified reference materials: water, riverine water, urine, bovine muscle and bovine liver. The agreement between obtained and certified concentrations was very good, except for As. The relatively small volume of methanol, used as eluent, minimizes the problems produced by the introduction of organic solvent into the plasma.     

Calculations and measurements of N2O absorption at high temperature in the 4.5 μm region

An approximate N₂O spectroscopic database suitable for high temperature and medium resolution applications has been created in the 4.5 μm region. Intensities of ¹⁴N₂ ¹⁶O hot bands have been extrapolated pragmatically from the v₃ band intensity and energies of vibrational levels have been computed by diagonalization of the effective Hamiltonian. The new parameters have been merged with the data available in the HITRAN database and in the recent experimental work of Toth. The entire list has then been used to generate individual line parameters. Pure N₂O spectra have been recorded with a Fourier Transform spectrometer up to 900 K and with 1 cm⁻¹ resolution. A good agreement between these spectra and line-by-line calculations using the new database is obtained while the use of HITRAN greatly underestimates absorption at high temperature.