天气型对北京地区近地面臭氧的影响

臭氧(O3)是夏秋季北京城市大气光化学污染物中的首要气态污染物,气象因素是影响其浓度水平和变化规律的主要因子之一.2008年7月~2008年9月,在北京市4个站点进行了臭氧、氮氧化物(NOx)和一氧化碳(CO)浓度的同步连续观测,并对同期天气型进行了分类比对分析.结果显示,观测期间,北京地区处于低压前部(主要是蒙古气旋)和高压前部的比例分别为42%和20%,分别是造成臭氧浓度高值和低值的主要背景场.处于低压前部控制时,高温、低湿以及局地环流形成的山谷风造成区域臭氧累积,小时最大值(体积分数)高达102.2×10-9,并随气压的升高以3.4×10-9Pa-1的速率降低,山谷风风向的转变决定了臭氧浓度最大值出现时间,峰值出现在14:00左右;处于高压前部控制时,低温、高湿以及系统性北风造成区域臭氧低值,小时最大值(体积分数)仅为49.3×10-9,系统性北风将臭氧峰值出现时刻推后到16:00左右.北京地区臭氧光化学污染呈现出区域一致性,并与天气型有较好相关,关注天气型结构和演变对预报大气光化学污染具有重要意义.     

光合有效辐射在大气中的衰减

2004年9月～2006年10月,在华北地区的4个站点开展了太阳辐射、气象参数等的综合观测,得到了光合有效辐射PAR、总辐射Q等的变化特征.水汽和散射因子对于PAR/Q和PAR有明显的影响.基于能量观点,建立了实际天气PAR小时累计值(时累)的经验模式,获得了较好的计算结果.水汽因子对于PAR在大气中的传输有一定的作用,应给予重视.计算表明,华北地区受水汽因子衰减到达地面的PAR以及占地面PAR的比例分别为7.99W.m-2和4.24%,受散射因子衰减到达地面的PAR以及占地面PAR的比例分别为172.36W.m-2和95.76%.华北地区受水汽因子和散射因子影响损失于大气中PAR分别为15.33、309.30W.m-2,这一能量损失表现出明显的季节变化和区域差别.敏感性实验表明,地表PAR对于水汽因子、散射因子的变化有不同的响应,PAR对散射因子的变化比对水汽因子的变化更敏感.水汽因子与PAR之间的关系与水密切相关,水汽因子项的真正含义应该是大气中的各种物质成分(气、液、固态)对于PAR的直接吸收和间接利用(通过化学和光化学反应,包括均相和非均相过程)的总和.利用PAR经验模式计算了大气顶的PAR,计算误差为-3.5%.在目前及未来研究中,应该重视和考虑消耗于大气中的且与水汽有关的这部分能量.基于能量观点分析实测资料并研究大气中的物理化学过程及其规律是一种行之有效的方法.     

Temporal variability of iron concentrations and fractions in wetland waters in Sanjiang Plain, Northeast China

Chemical forms, reactivities and transformation of iron fractions in marshy waters were investigated with cross-flow filtration technique to study the iron environmental behavior. Iron fractions were divided into four parts: acid-labile iron (pre-acidification of unfiltered marshy water samples, 0.7 μm), high-molecular-weight iron (0.7-0.05 μm), medium-molecular-weight iron (0.05-0.01 μm), and low-molecular-weight iron ( 0.01 μm). The cross-flow filtration suggested that iron primarily exist in both the 0.7 μm and 0.01 μm size fractions in marshy waters. Rainfall is the key for rain-fed wetland to determine fate of iron by changing the aquatic biochemical conditions. By monitoring the variation of iron concentrations and fractions over three years, it was found that dissolved iron and acid-labile iron concentrations exhibit a large variation extent under different annual rainfalls from 2006 to 2008. The seasonal variation for iron species proved that the surface temperature could control some conversion reactions of iron in marshy waters. Low- molecular-weight iron would convert to acid-labile iron gradually with temperature decreasing. The photochemical reactions of iron fractions, especially low-molecular-weight iron had occurred under solar irradiation. The relative proportion of low-molecular-weight in total dissolved iron ranging from 28.3% to 43.2% were found during the day time, which proved that the observed decreasing concentration of acid lability iron was caused by its degradation to low molecular weight iron.     

烟雾箱模拟乙炔和NOx的大气光化学反应

利用自制光化学烟雾箱进行了一系列表征实验并模拟了乙炔和氮氧化物NO_x在室温（20±1）℃下的大气光化学反应．讨论了乙炔与NO_x的协同作用对光化学反应产生O₃的影响．实验得到了O₃和NO₂的壁损失分别为5.80×10^-6 s^-1和2.41×10^-6 s^-1,相对于模拟实验中的O₃和NO₂,该损失可以忽略．测得了单支40 W黑光灯的有效光强为0.64×10^-3 s^-1（以NO₂的光解速率表示）．经过净化空气的本底校正后,讨论了不同乙炔浓度、NO_x浓度以及光照强度对体系产生O₃的影响,计算了乙炔的增强反应活性值（incremental reactivity, IR）,4组实验的IR最大值分别为1.76×10^-2、2.68×10^-2、2.04×10^-2和2.84×10^-2．并发现IR值与乙炔的初始浓度以及光照强度关系密切,与NO_x初始浓度关系不大．     

北京大气中NO、NO2和O3浓度变化的相关性分析

臭氧（O₃）是城市污染大气中的首要光化学污染物,其变化规律与氮氧化物(NO_x=NO+NO₂)关系密切.采用49C臭氧分析仪和42CTL氮氧化物分析仪对北京城区O₃和NO_x浓度进行了连续观测,时间为2004-08～2005-07.结果显示,O₃和OX（O₃+NO₂）浓度在午后15:00左右出现峰值,NO_x呈双峰态日变化,在07:00和23:00左右出现峰值.不同季节污染物的浓度变化存在差异,O₃和NO_x浓度分别在夏季和冬季达到最大.NO_x浓度存在100×10^-9(体积分数)的“分界点”,NO_x低浓度时以NO₂为主,NO_x高浓度时NO占大部分.OX区域贡献和局地贡献存在明显的季节变化,前者主要受区域背景O₃的影响,在春季最大,后者主要受局地NO_x光化学反应的制约,在夏季最强,同时OX组分呈现显著的昼夜差异.     

Applying model simulation and photochemical indicators to evaluate ozone sensitivity in southern Taiwan

Ozone sensitivity was investigated using CAMx simulations and photochemical indicator ratios at three sites (Pingtung City, Chao- Chou Town, and Kenting Town) in Pingtung County in southern Taiwan during 2003 and 2004. The CAMx simulations compared fairly well with the hourly concentrations of ozone. Simulation results also showed that Pingtung City was mainly a volatile organic compounds (VOC)-sensitive regime, while Chao-Chou Town was either a VOC-sensitive or a NOx-sensitive regime, depending on the seasons. Measurements of three photochemical indicators (H2O2, HNO3, and NOy) were conducted, and simulated three transition ranges of H2O2/HNO3 (0.5–0.8), O3/HNO3 (10.3–16.2) and O3/NOy (5.7–10.8) were adopted to assess the ozone sensitive regime at the three sites. The results indicated that the three transition ranges yield consistent results with CAMx simulations at most times at Pingtung City. However, both VOC-sensitive and NOx-sensitive regimes were important at the rural site Chao-Chou Town. Kenting Town, a touring site at the southern end of Taiwan, was predominated by a NOx-sensitive regime in four seasons.     

氟啶虫胺腈在不同有机溶剂中的光化学降解

利用液质联用和气相色谱（HPLC-Mass和GC）,研究了氟啶虫胺腈在两种不同光源下于4种不同溶剂（正己烷、甲醇、乙腈、丙酮）中的光化学降解.结果表明,以氙灯为光源,1.0、5.0、20.0mg·L-1的氟啶虫胺腈在4种溶剂中的降解半衰期分别为11.62、8.33、10.80h（正己烷）,5.30、5.81、7.05h（甲醇）,1.72、1.99、2.79h（乙腈）,83.49、37.46、64.77h（丙酮）.以紫外灯为光源,1.0、5.0、20.0mg·L-1的氟啶虫胺腈在4种溶剂中的降解半衰期分别为5.29、4.25、5.49min（正己烷）,2.19、2.97、5.88min（甲醇）,0.86、1.99、1.13min（乙腈）,330、365、198min（丙酮）.氟啶虫胺腈的降解反应主要为还原、水解反应,影响其降解速率的主要因素是光源和溶剂的种类,氟啶虫胺腈的浓度对其降解速度也有一定影响.     

A VUV photoionization mass spectrometric study on the OH-initiated photooxidation of isoprene with synchrotron radiation

The gas-phase organic compounds resulting from OH-initiated photooxidation of isoprene have been investigated on-line by VUV photoionization mass spectrometry based on synchrotron radiation for the first time. The photoionization efficiency curves of the corresponding gaseous products as well as the chosen standards have been deduced by gating the interested peaks in the photoionization mass spectra while scanning the photon energy simultaneously, which permits the identification of the pivotal gaseous products of the photooxidation of isoprene, such as formaldehyde (10.84 eV), formic acid (11.38 eV), acetone (9.68 eV), glyoxal (9.84 eV), acetic acid (10.75 eV), methacrolein (9.91 eV), and methyl vinyl ketone (9.66 eV). Proposed reaction mechanisms leading to the formation of these key products were discussed, which were completely consistent with the previous works of different groups. The capability of synchrotron radiation photoionization mass spectrometry to directly identify the chemical composition of the gaseous products in a simulation chamber has been demonstrated, and its potential application in related studies of atmospheric oxidation of ambient volatile organic compounds is anticipated.     

珠江三角洲大气光化学氧化剂(Ox)与PM2.5复合超标污染特征及气象影响因素

基于粤港澳珠江三角洲区域空气监测网络12个监测子站的大气污染物数据,梳理2013~2017年大气光化学氧化剂O_x（NO₂+O₃）与PM_2.5质量浓度的变化趋势.O_x+PM_2.5复合超标污染定义为NO₂和PM_2.5质量浓度日平均值以及O₃浓度日最大8 h平均值（O₃ MDA8）同时超过二级浓度限值,分析了不同类型站点复合超标污染的时空分布特征以及气象因素影响.结果表明,2013~2017年珠三角PM_2.5年均质量浓度由（44±7）μg·m^-3下降至（32±4）μg·m^-3,实现PM_2.5连续3 a达标.O_x年均质量浓度由2013年（127±14）μg·m^-3下降至2016年（114±12）μg·m^-3,2017年反弹至（129±13）μg·m^-3,O₃浓度上升明显（10 μg·m^-3）.以O₃为首要污染物的污染过程占比由2013年33%增多至2017年78%,多个城市同时发生污染的区域特征明显.研究时段内O_x+PM_2.5复合超标污染事件共发生60次,主要在城区站点（78%）和郊区站点（22%）.秋季发生复合超标污染天数最多（52%）,是因为强太阳辐射有利于臭氧生成,大气氧化性增加,进而促进了PM_2.5二次生成.造成珠三角复合超标污染的天气形势主要为高压出海型（43%）、高压控制型（30%）和热带低压型（27%）.就具体气象因素而言,气温在20~25℃且相对湿度在60%~75%的范围内时,复合超标污染事件发生占比最高（22%）.在O₃重污染过程中,夜间高湿和低风速使得NO₂和PM_2.5浓度显著上升,日间高温加剧了复合超标污染.     

株洲市臭氧污染状况及相关气象因子分析

采用2013年1～12月空气质量自动监测数据对株洲市臭氧污染现状及相关气象因子进行分析。结果表明:监测期间全年臭氧日最大8 h平均浓度一级标准值达标率达到71.8%,全年超标率为1.6%,超标主要出现在季节变换时期。臭氧日最大8 h平均浓度的月均值变化呈"M"型,浓度高值持续时间长。日变化规律较强,且不同季节变化特征略有差别。臭氧浓度与气温有正相关性,相关系数为0.612;与湿度和云量有负相关性,且臭氧与湿度负相关性较明显,相关系数为0.731。