Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.     

Photodegradation of butyl acrylate in the troposphere by OH radicals: kinetics and fate of 1,2‐hydroxyalcoxy radicals

The rate constant of the reaction of OH radicals with butyl acrylate was studied for the first time using an atmospheric simulation chamber at 298 K and ～750 Torr of air or nitrogen. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC‐FID), and the rate constant was determined using a relative rate method with different references. The obtained average value of (1.80 ± 0.26) × 10^?11 cm³ molecule^?1 s^?1 is in agreement with previous determinations of the rate constants of OH radicals with acrylates and methacrylates in the literature. Additionally, product identification under atmospheric conditions was performed for the first time by the GC‐MS technique. Butyl glyoxalate was observed as the degradation product in accordance with the addition of OH to the less substituted carbon atom of the double bond, followed by decomposition of the 1,2‐hydroxyalkoxy radicals formed. Room temperature rate coefficient was used to estimate the atmospheric lifetime of the ester studied. Reactivity trends are discussed in terms of the substituent effects and the length of the hydrogenated chain of the ester. The atmospheric persistence of BUAC was calculated taking into account the experimental rate constant obtained. Copyright © 2008 John Wiley & Sons, Ltd.     

双差分测量对流层臭氧的实验研究

 提出了利用266nm,289nm,308nm三波长进行臭氧测量的数值模拟和实际测量实验研究。三波长双差分和双波长差分的模拟实验结果表明,当对流层气溶胶分布相当不均匀,后向散射比梯度较大时,气溶胶对双波长差分测量臭氧影响很大,而对三波长双差分测量臭氧影响较小。     

探测对流层气溶胶的双波长米氏散射激光雷达

研制了一台双波长米氏散射激光雷达,用于532nm和1064nm两个波长对流层气深胶消光系数垂直廓线的长期探测.介绍了该激光雷达的技术参数和总体结构,叙述了各部分的结构和工作原理,给出了合肥地区对流层气溶胶测量的若干典型结果.     

顾及高程差异的网络差分对流层误差内插模型

在GPS网络差分定位技术中,用户站与参考站间的高程差异会引起对流层误差改正数中存在系统性偏差,造成对流层改正精度降低,影响用户定位的效果。在常规两维线性组合模型的基础上,考虑高程因素影响,利用三维位置信息对内插模型参数进行约束,将对流程延迟改正数分为距离相关和高程相关两部分,通过卡尔曼滤波器分别估计,提出了一种能修正高程偏差的对流层三维线性组合模型。以重庆连续运行参考站系统中5个站作为研究对象,实验验证结果表明,在地形起伏较大的地区,三维线性组合模型可将对流层改正精度从20～40 cm提高到5～6 cm,相对于常规方法提高了4～6倍,消除了网络差分定位中高程差引起的对流层改正系统偏差。     

机载腔增强吸收光谱系统应用于大气NO_2空间高时间分辨率测量

介绍了一套用于机载平台测量的非相干宽带腔增强吸收光谱(IBBCEAS)系统,并应用于实际大气NO_2空间分布的高时间分辨率观测.为满足机载测量中对时间分辨率的需求,系统采用离轴抛物面镜代替消色差透镜提高光学耦合效率;并运用Allan方差,对系统性能进行了分析.通过腔增强吸收光谱系统与长光程吸收光谱系统对实际大气NO_2的对比测试,两者线性相关系数R~2达到0.86.将IBBCEAS系统应用于机载平台,在时间分辨率为2 s的情况下,探测限达到95 ppt(1σ).通过机载观测,获得了华北地区石家庄等地上空对流层大气NO_2的廓线信息.     

机载多轴差分吸收光谱技术获取对流层NO2 垂直柱浓度的研究

介绍了一种基于机载平台获取对流层NO₂垂直柱浓度的多轴差分吸收光谱技术. 研究了利用差分吸收光谱技术结合不同观测角度的测量光谱反演差分斜柱浓度, 并利用辐射传输模型SCIATRAN计算对流层NO₂垂直柱浓度的方法. 研究了不同海拔高度、不同地面反照率以及不同太阳天顶角等条件对天顶和天底两个观测角度的大气质量因子的影响. 报道了该系统在2008年12月10日在珠三角地区的实验结果, 结合天顶和天底两个方向反演得到了珠三角地区对流层NO₂垂直柱浓度的分布信息. 同时还将机载测量结果跟安装在珠海市的一台地基多轴差分吸收光谱仪的结果进行了对比, 二者相差仅为8%. 实验结果表明, 机载多轴DOAS技术可以实现对大区域对流层NO₂浓度的快速获取.     

基于三级Fabry-Perot标准具的纯转动拉曼测温激光雷达

提出了新的纯转动拉曼测温雷达系统,即以种子激光注入锁定的Nd:YAG激光器为激发光源,采用基于三级Fabry-Perot(F-P)标准具的双通道分光结构代替双光栅单色仪结构.通过通道中宽带滤光片(带宽为7nm)及F-P标准具的组合使用,对532nm激发光的大气Mie-Rayleigh弹性回波散射抑制比可达10^-10,对量子数J=±6,J=±12的N₂纯转动拉曼散射光谱线接收带宽均小于10pm,因此能充分抑制大气背景辐射噪声及O₂纯转动拉曼谱线的干扰,从而实现了单谱线比反演温度,提高了探测精度,且可在白昼探测大气对流层温度.最后通过探空气球测得的对流层温度垂直分布逆向模拟了该系统双通道的Raman信号曲线,证实了该系统的可行性. 关键词： 拉曼激光雷达 纯转动拉曼散射 三级Fabry-Perot标准具 对流层     

VERTICAL DISTRIBUTION OF ATMOSPHERIC AEROSOL CONCENTRATION AT XIANGHE

1. Introduction In 1984, we started a Sino-Japanese joint balloon pro-gram to measure troposphere and stratosphere aerosols.The program was collaboratively executed by the Instituteof Atmospheric Physics (IAP), Chinese Academy of Sci-ences (CAS), and Research Institute of Atmospherics,Nagoya University, Japan (Shi et al., 1987). In 1993, 1994and 1997, the program was carried out by IAP, Anhui In-stitute of Optical and Fine Mechanics (AIOFM), CAS, andGraduate School of Environ…     

INVESTIGATIONS OF MAIN FACTORS AFFECTING TROPOSPHERIC NITRATE AEROSOL USING A COUPLING MODEL

1. Introduction As the main chemical product from nitric acid (HNO3), ammonia (NH3) and sodium chloride (NaCl) in the tropo-sphere, nitrate (NO3-) is a kind of secondary inorganic aerosol. Considering the atmospheric environment, nitrate aerosol is one of the essential components of fine particu-lates, such as PM2.5, which adversely affect visibility and human health. In recent years, due to rapid industrializa-tion and urbanization, nitrous oxide (NOX) emissions from industry and transp…