异戊二烯和甲苯二次有机示踪物的臭氧非均相氧化

本文基于相对速率法,通过烟雾箱实验测定了异戊二烯和甲苯二次有机示踪物的臭氧非均相氧化的有效速率常数,考察了不同条件(相对湿度和混合状态等)对示踪物臭氧非均相氧化过程的影响,并且分析了由于示踪物被氧化所引起的二次源解析的不确定性.结果表明,赤藓糖醇(analogue of 2-methyl erythritol,AME)和2,3-二羟基-4-氧代戊酸(2,3-dihydroxy-4-oxopentanoic acid,DHOPA)的有效速率常数分别为(4. 60±0. 66)×10-19cm~3·(molecule·s)~(-1)和(6. 57±0. 51)×10-19cm~3·(molecule·s)~(-1);考虑到示踪物不稳定引起的不确定性,采用示踪物产率法解析二次源会对异戊二烯和甲苯二次生成气溶胶低估约16. 5%～44. 8%和18. 3%～47. 3%.     

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．     

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。     

长光路FTIR研究OH发生体系中的OH浓度

利用长光路ＦＴＩＲ测定早苯、三本等芳香烃化合物在烟雾箱中光化学反应衰减,确字了ＮＯｘ－Ｈ２Ｏ、Ａｉｒ、ＨＯＮＯ－Ｈ２Ｏ－Ａｉｒ和ＣＨ３ＯＮＯ－ＮＯ－Ａｉｒ３种体系在我灯自夸下的ＯＨ浓度,结果表明三者ＯＨ浓度范围分别为：～１０＾５～１０＾６、～１０＾７、～１０＾７～１０＾８ｍｏｌｅｃｕｌｅｓ．ｃｍ＾－３,并进一步讨论了反应前体物对生成ＯＨ浓度的影响。     

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.     

珠江三角洲一次典型复合型污染过程的模拟研究

利用空气质量模式系统(MM5-CAMQ-SMOKE),模拟珠江三角洲一次典型的复合型污染过程,研究O3、NOx及能见度等的时空变化,分析各种气溶胶的质量比例以及对消光的贡献.从模拟结果来看,模式系统能很好的模拟此次过程中光化学烟雾标识物的时空分布,以及灰霾的发生、减弱再到进一步加剧的过程.PM2.5占PM10的质量浓度份额平均为79.8%.爱根核和积聚核的数浓度比巨核数浓度平均高3~4个数量级.在气溶胶质量权重中,硫酸盐所占的比重最高,占PM2.5权重达到31%,元素碳为21%,有机碳为14%,铵盐为7.2%,硝酸盐为2%.在平均相对湿度下,二次气溶胶对消光的贡献超过50%,而在高相对湿度的情况下,二次气溶胶对消光的贡献超过70%.可见此次珠江三角洲地区能见度恶化主要是由各种化学过程生成的细粒子引起.     

The traffic emission and its impact on air quality in Guangzhou area

A comprehensive field measurement was set up in Guangzhou City of China and the key was placed on NO_x and O₃ pollution. The results indicated that the average driving speed of vehicle was only 14 km/h in downtown with high frequency of idle and acceleration. Upward fluxes of CO and NO were observed in Dongfeng street. NO_x annual mean concentration in urban area increased year by year, and NO_x was identified as the most important pollutant since 1995. Photochemical smog pollution was serious in general,spatial and seasonal distribution of O₃ was observed. O₃ concentration was kept in a high level in autumn, and its formation was restrained in summer due to frequent thunderstorm and high humidity. The numerical simulation showed the average concentration and maximum concentration of O₃ would increase 60%—100% if vehicular emission increased 100% in Guangzhou.     

雾霾污染的空间外溢与治理政策的检验分析

以2006~2016年城市层面数据为样本,结合空间扩散效应深入探究雾霾污染的影响机理,并对已出台治霾政策的治理效果和传导机制进行识别.研究发现：考察期内我国雾霾污染具有一定时滞性、空间相关性和时空“警示作用”;以往环境规制由于诱发污染产业地区间就近转移对减霾贡献并未达到预期效果.“大气十条”的治霾效果明显,到2016年该政策的实施使重点关注的三大经济带PM_2.5显著降低约7.1%,其中,中部和东部区域政策实施城市治理效果最为显著;政策实施以来各地区环保部门通过对重污染企业的限产整治取得了降霾的短期治理效果,但对重污染企业的创新激励传导作用并不显著.因此,未来雾霾治理政策更需注重如何通过激发企业绿色技术创新从而建立根治雾霾污染的长效机制.     

Particle number concentration, size distribution and chemical composition during haze and photochemical smog episodes in Shanghai

The aerosol number concentration and size distribution as well as size-resolved particle chemical composition were measured during haze and photochemical smog episodes in Shanghai in 2009. The number of haze days accounted for 43%, of which 30% was severe （visibility 〈 2 km） and moderate （2 km 〈 visibility 〈 3 km） haze, mainly distributed in winter and spring. The mean particle number concentration was about 17,000/cm3 in haze, more than 2 times that in clean days. The greatest increase of particle number concentration was in 0.5-1μm and 1-10 μm size fractions during haze events, about 17.78 times and 8.78 times those of clean days. The largest increase of particle number concentration was within 50-100 nm and 100-200 nm fractions during photochemical smog episodes, about 5.89 times and 4.29 times those of clean days. The particle volume concentration and surface concentration in haze, photochemical smog and clean days were 102, 49, 15 μm3/cm3 and 949, 649, 206 μm2/cm3, respectively. As haze events got more severe, the number concentration of particles smaller than 50 nm decreased, but the particles of 50-200 nm and 0.5-1μm increased. The diurnal variation of particle number concentration showed a bimodal pattern in haze days. All soluble ions were increased during haze events, of which NH4, SO24- and NO3 increased great/y, followed by Na＋, IC, Ca2＋ and CI-. These ions were very different in size-resolved particles during haze and photochemical smog episodes.     

基于大数据分析的雾霾污染预测研究

对雾霾的监控预测已成为城市重点监测指标,传统雾霾监测方法使用的是高斯预测模型,在预测过程中会使用大量的参数以及逻辑关系,在大数据分析的趋势下已经不能承接海量相关大数据,针对上述问题,提出一种基于大数据分析的雾霾污染预测方法.建立数据K模型承接海量数据,对大数据特点趋势加以分析,使用组合算子对雾霾污染度预测,摒弃逻辑关系束缚以及大数据的驱使性,对特征数据进行类别掌控完成预测结果.通过对比实验的方式对提出的方法进行检验,实验结果表明:(1)基于大数据分析的雾霾污染预测方法能够在大数据环境下对雾霾污染度进行高精度预测;(2)与传统方法相比较能够承接大数据的变化;(3)摒弃逻辑关系的制约可以实现随时预测;(4)极大的缩减预测成本.