中国典型城市臭氧与二次气溶胶的协同增长作用分析

大气PM_2.5和O₃是中国城市大气中最受关注的大气污染物,它们之间存在着复杂的影响关系.本文将O_3,max作为光化学活性指标,把CO作为一次排放源的示踪剂,对2017年4—10月期间北京、上海和广州的臭氧与二次气溶胶的协同增长关系进行深入分析.研究结果表明,不同光化学活性条件下,3个城市在协同增长时段PM_2.5质量浓度增长量的均值与估算二次气溶胶质量浓度的变化趋势基本一致;北京和广州在春季、秋季出现协同增长的小时数较多,且北京在各光化学活性水平下的协同增长时段中PM_2.5浓度增长量均最大;出现PM_2.5和O₃协同增长现象时段中上海市风速最大,广州市气温最高,北京市相对湿度范围最大;随着光化学活性的增强,上海和广州两市二次气溶胶的生成量呈倍数增加,其生成量范围分别为13.6~29.2 μg·m^-3和9.1~28.7 μg·m^-3,北京市二次气溶胶的生成量则变化不大（25.0~34.0 μg·m^-3）,但各光化学活性水平下的北京二次气溶胶生成量均高于上海和广州.这些研究结果表明北京、上海和广州3个城市的O₃污染对二次气溶胶生成协同增长作用明显,而且北京尤其值得关注.     

生物酶强化厌氧消化去除污泥中的PhACs

为降低污水污泥中药理活性化合物（PhACs）产生的环境风险,利用生物方法强化污泥厌氧消化,提高其去除效果.以CFA（氯贝酸）、TCS（三氯生）、DCF（双氯芬酸）、CBZ（卡马西平）4种典型的PhACs为目标污染物,利用气相色谱-质谱联用仪（GC-MS）定量分析污泥中的目标物,探究外加生物酶联合污泥厌氧消化法强化对PhACs的作用效果.结果表明,随着SRT（污泥停留时间）的增大,目标物的去除率有一定程度的增大,特别是在高温条件下,当SRT由7 d增至20 d时,CFA的去除率增长了45%;木瓜蛋白酶对中高温系统中CBZ的去除效果最佳,分别为63.8%和67.5%,同时对4种目标物总的去除率最高,分别为57.3%和61.8%;添加溶菌酶试验中,4种目标物去除效果差异较大,中温、高温系统中对TCS的去除效果最佳为81.7%和80.9%,去除效果最差的是CBZ,去除率为40.4%和33.5%;纤维素酶处理中,4种目标物的去除率均小于60%.混合生物酶试验中,高温条件下更易去除PhACs.研究显示,生物酶强化污泥厌氧消化能有效去除污水污泥中的PhACs.      

二甲亚砜捕获-高效液相色谱测定天然水体中羟基自由基的光化学生成

利用二甲亚砜捕获羟基自由基定量生成甲醛,甲醛与1,3-环己二酮和氨衍生反应,衍生产物在400 nm的激发波长下,在460 nm处具有特征荧光,建立了一个新的高效液相色谱分离、荧光检测水体中光学反应产生的羟基自由基的方法.考察了捕获剂用量、酸度、温度、时间以及衍生试剂用量对羟基自由基测定的影响,在优化的实验条件下,该方法对羟基自由基的定量下限为0.066μmol·L-1.采用建立的方法对湖水、海水以及湿地水在氙灯模拟光源以及太阳光下羟基自由基光化学生成进行了初步研究,表明太阳光照下羟基自由基的生成速率约为氙灯光照下羟基自由基生成速率的两倍以上,说明羟基自由基在实际自然条件下的生成速率有可能被低估.天然水体中的羟基自由基的生成与水体成分密切相关,由铁和可溶性有机质(DOM)光照产生羟基自由基的机理较为复杂,DOM和铁的相互作用对天然水体中羟基自由基的光化学生成影响有待于进一步研究.     

Peroxyacetyl nitrate observed in Beijing in August from 2005 to 2009

Measurements of peroxyacetyl nitrate（PAN） were made at a Beijing urban site each August from2005 to 2009. Over this 5-year period, the average PAN concentration for August in each year increased from 3（2005） to 11.7 μg/m3（2007）; however, it decreased rapidly in 2008（4.1 μg/m3）.Generally, the variation over the 5 years showed a rise in the first part of the study period,followed by a decline. We considered two categories of local and regional air masses in this study, which revealed that the PAN concentration in Beijing was affected mainly by southeastern air masses. The August PAN variation was influenced predominantly by local air masses in 2005,but by 2009 regional air masses had become more important. This study showed the level and variation of PAN in the month of August in 5 consecutive years for the first time, and proved that control measures are useful in decreasing photochemical pollution; hence, these measures are probably feasible for other megacities too. Furthermore, this method of analyzing regional and local impacts might be useful for other studies as well.     

Wintertime peroxyacetyl nitrate (PAN) in the megacity Beijing: Role of photochemical and meteorological processes

Previous measurements of peroxyacetyl nitrate(PAN) in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site(CMA) in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10 9mol/mol(0.23 × 10 9–3.51 × 10 9mol/mol) and was well correlated with that of NO2but not O3, indicating that the variations of the winter concentrations of PAN and O3in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3ratio smaller than 0.031, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl(PA) radical was estimated to be in the range of 0.0014 × 10 12–0.0042 × 10 12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN's variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.     

Characteristics of ozone and ozone precursors (VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors(VOCs and NOx) was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface O3 pollution with the characteristics of high average daily mean and maximum concentrations(64.0 and 145.4 ppbV in no-rain days, respectively) and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.5–46.1 and 1.8–6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes(60.0% ± 4.3%), alkenes(21.1% ± 5.5%) and aromatics(18.9% ± 3.9%). Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15–0.27 and 0.42–0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.     

几种光化学体系中自由基的产生和测定

在人工光源照射下，以水杨酸为探针性物质，探讨了过氧化氢，二氧化钛，亚硝酸钠，硝酸钠和杂多酸盐等５种光化学体系中羟自由基的产生，并测定了羟自由基的稳态浓度。     

一种香兰素的制备方法

该发明公开了一种香兰素的制备方法。其方法：将制浆废液中的木质素磺化得到的木质素磺酸盐溶于水，然后将得到的溶液置于光化学反应器中，在半导体光催化剂（其加入量为上述水溶液质量的0．5％～1％。）的作用下，通入空气或氧气，用紫外灯在常温至80℃的温度下辐照进行光催化氧化降解，分离后得到香兰素产品。     

污染物在冰晶中的光化学研究进展

从冰晶的性质、冰晶中的光化学反应和光化学反应机理、对环境的影响以及研究过程中遇到的困难,对污染物在冰晶中的光化学进行了探讨,为开展这方面的工作提供信息.     

北京大气O3与NOx的变化特征

以2004年8月-2005年7月北京市区近地层大气中臭氧(O3)和氮氧化物(NOx)体积分数观测资料,研究了北京大气中O3和NOx体积分数的变化特征.研究表明:北京市O3体积分数较高,并呈季节性波动,大气光化学污染以夏季最为严重.受太阳紫外辐射和城市交通的影响,城市O3体积分数呈单峰型分布,并在午后15:00出现峰值,造成大气强氧化性.NO2的光解速率夏季最大,在正午出现日最大值.受城市车流量变化的影响,周末NOx体积分数高于工作日,O3体积分数周末与工作日白天差异较小,而夜晚O3体积分数上作日高于周末.