日盲紫外域拉曼激光雷达探测大气水汽技术研究

拉曼激光雷达通过探测与水汽浓度相关的大气水汽振动拉曼散射回波信号,可实现大气水汽混合比廓线的探测。然而由于振动拉曼信号非常微弱,在白天测量时振动拉曼散射光谱会淹没在太阳背景光中,多在夜间测量。为实现大气水汽的全天时测量,设计开发一套日盲紫外波段拉曼激光雷达系统。该系统选择Nd∶YAG脉冲激光器的四倍频输出-266.0 nm日盲紫外波段作为拉曼激光雷达系统的激励波长,采用镀高增益介质膜的牛顿式望远镜作为接收器,同时利用二向色镜和超窄带干涉滤光片设计高效率的高光谱分光系统,实现了大气氧气、氮气和水汽振动拉曼散射回波信号277.5,283.6和294.6 nm的精细提取。计算仿真结果表明,臭氧吸收对日盲紫外域拉曼激光雷达探测存在一定的影响,主要是探测距离的影响;氮气通道不受白天太阳背景光噪声的影响;水汽通道存在少量太阳背景光噪声,对系统探测距离略有影响。而系统信噪比计算结果表明,设计的日盲紫外域拉曼激光雷达系统可实现白天3.5 km大气水汽的探测。实际进行水汽探测时,可利用氮气和氧气通道反演出臭氧浓度廓线,修正臭氧对发射波长、各通道拉曼散射波长的吸收,进一步提升系统的探测能力和探测精度。     

Sequential Injection Chemiluminescence Methodology for Ozone Evaluation

A sequential injection methodology with chemiluminescence detection for the evaluation of residual ozone in waters is presented. The procedure is based on the reaction between luminol and ozone without catalysts.

Linear calibration plots were obtained for ozone concentrations between 0.05 and 2.0 mg L^?1, with a detection limit of 0.04 mg L^?1.

The developed methodology was applied to the determination of residual ozone in ozonized waters and the results complied with those furnished by the spectrophotometric reference procedure (relative deviations < 6.3%). The method exhibited good precision (RSD < 3.5%) and the sampling rate was about 140 determinations per hour.     

黑碳颗粒物表面SO2的非均相臭氧氧化

采用漫反射红外傅里叶变换光谱(DRIFTS)结合离子色谱(IC)、 X射线光电子能谱(XPS)研究了常温常压下SO2与O3在黑碳颗粒物(以Printex U为代表, 简称UBC)表面的非均相反应. 研究发现, 在O3和水气存在的情况下, 体系的反应产物主要是SO42-, 反应在一定时间内持续进行. UBC可提供反应活性位点, 促进SO2在其表面的臭氧氧化. O3是关键的氧化剂, 能显著提高SO2非均相氧化生成SO42-的速率. 水气的存在有利于表面活性位点再生, 使反应持续发生. 当SO2和O3的浓度为1014~1015 molecule/cm3、 相对湿度为40%时, SO2在UBC(1: 400, 以NaCl为稀释剂稀释400倍)表面非均相反应生成SO42-的稳态摄取系数(γBET)为1~6×10-6, SO42-的生成速率为1014~1015 ion·s-1·g-1.     

Comparison of analytical methods for ozone precursors using adsorption tube and canister

Recently, ozone concentrations have increased dramatically as a result of vehicle usage in metropolitan areas. Ozone precursors are composed of hydrocarbons of organic compounds. Because hydrocarbons are indicative of ozone formation, they need to be monitored in ambient air. Since ozone precursor are present at very low levels (from ppb to ppt) in ambient air, they are difficult to analyze accurately. This study investigates ozone precursors in ambient air. The main purpose of this study is to compare analytical methods for the measurement of ozone precursors in atmosphere. Two measurement methods were evaluated using canister (Silco-canister) and adsorbent (300-mg Carbopack B+150-mg Carbosieve SIII) tube. Differences in measurements for total ozone precursor emissions were 54.1% between the adsorption tube and canister-GC/MS, 51.1% between adsorption tube and canister-GC/FID, and 16.3% between canister-GC/MS and canister-GC/FID.     

臭氧与二乙胺和三乙胺气相反应的速率常数

利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学. 实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度, 使得实验在准一级条件下进行. 加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响. 在(298±1) K和1.01×105 Pa条件下, 测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10^-17和(8.20±1.01)×10^-17 cm³·molecule^-1·s^-1. 与文献中已有的其它胺类的臭氧反应数据比较后发现, 臭氧与胺的反应可以用亲电反应机制来解释. 另外, 通过对比发现, 臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率. 这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实. 利用测得的速率常数和大气中臭氧浓度, 还估算了二乙胺和三乙胺与臭氧反应的大气寿命. 结果显示, 与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径, 尤其是在污染严重地区.     

乙烯自由基与臭氧反应的DFT计算研究

采用密度泛函B3LYP/6-311G**水平计算研究了O3氧化乙烯基（C2H3）的机理,全参数优化了反应势能面上各驻点的几何构型,用内禀反应坐标（IRC）计算和频率分析方法,对过渡态进行了验证.结果表明，乙烯基（C2H3）与O3之间有很强的反应活性.     

Ionization of Ozone/Chlorofluorocarbon Mixtures in Atmospheric Gases: Formation and Dissociation of [CHX2O3]+ Complexes (X=Cl,F)

Complexes that undergo extensive molecular reorganization upon unimolecular metastable dissociation are obtained after ionization of atmospheric gases containing ozone and chlorofluorocarbons [Eq. (1)]. These unusual processes, which require fission of all bonds initially present in the CHX₂ unit (X=Cl, F) and combination of C with one of the O atoms of ozone, were demonstrated and their mechanism rationalized by the joint application of mass spectrometric and theoretical methods.     

Intercomparison of ozone profiles measurements by a differential absorption lidar system and satellite instruments at Buenos Aires, Argentina

A ground-based DIfferential Absorption Lidar (DIAL) system has been implemented at CEILAP (CITEFA-CONICET) laboratory (34°33′S, 58°30′W), located in the Buenos Aires industrial suburbs. The goal is to perform measurements of the stratospheric ozone layer. Systematic measurements of ozone concentration profiles from 18 to 35 km altitude are performed since early 1999. Our measurements are carried out in 5 h in average during the night and in cloudless conditions. The DIAL system allows us to calculate directly the ozone profile from the lidar backscattering radiation since it is a self-calibrating technique. The signal processing takes into account the influence of the temperature profile on the ozone cross section. The temperature data are obtained from the radiosondes measurements performed at Ezeiza International Airport (34°30′S, 58°18′W), 27 km from DIAL station. The evolution of the stratospheric ozone profile is studied for different months. Results are compared with the data obtained by different satellites SAGE II, HALOE and GOME. The comparisons between our DIAL system and the satellite measurements show an agreement better than 20% for 20–35 km altitude range.     

臭氧与二乙胺和三乙胺气相反应的速率常数

利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学. 实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度, 使得实验在准一级条件下进行. 加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响. 在(298±1) K和1.01×105 Pa条件下, 测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10^-17和(8.20±1.01)×10^-17 cm³·molecule^-1·s^-1. 与文献中已有的其它胺类的臭氧反应数据比较后发现, 臭氧与胺的反应可以用亲电反应机制来解释. 另外, 通过对比发现, 臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率. 这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实. 利用测得的速率常数和大气中臭氧浓度, 还估算了二乙胺和三乙胺与臭氧反应的大气寿命. 结果显示, 与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径, 尤其是在污染严重地区.     

CFC phase-out: have we met the challenge?

In 1974 Nobel prize winners Rowland and Molina proposed that chlorofluorocarbons (CFCs) were stable enough to reach the stratosphere, where, under intense solar radiation they released Cl atoms that could destroy stratospheric ozone protecting the earth’s surface from UV rays. The CFC industry funded both scientific studies to test the Rowland and Molina hypothesis and programmes to identify potential replacements, from which the HFCs emerged as likely candidates. After 5 years it was concluded, on the best scientific evidence available, that stratospheric ozone was being depleted at ∼3% per decade, but sufficient time was available for an orderly phase-out. Although the USA and a few other countries stopped the use of CFCs in aerosols little further work was done until 1985 when the CFC debate was renewed following the discovery of stratospheric ozone depletion over the Antarctic during its spring. Manufacturers restarted their R&D programmes; governments negotiated the Montreal Protocol in 1987 agreeing the partial phase-out of the CFCs. As a result of subsequent amendments CFCs have now been phased-out in the developed world and HCFCs will follow over the next two decades. This paper reviews what has been achieved and what remains to be done. Has the world-wide effort been successful in protecting the ozone layer? Have “acceptable” alternatives been found for the CFCs/HCFCs in their various applications?