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.     

紫外光降解黑索金(RDX)的研究

本课题对模拟废水中RDX在紫外光和氧化剂等作用下的光化学降解情况进行了研究.运用正交设计法来安排实验,获得了废水的酸碱度、过氧化氢与亚铁离子的投加量、紫外光照射的时间等RDX降解的最佳条件.自行设计了光化学降解装置.在最佳条件下对RDX模拟废水进行光化学处理,并利用721分光光度计以及TOC-500测试仪对实验结果进行鉴定,取得了较为满意的结果.     

厦门市光化学污染研究

根据2012年厦门市区空气中O3的监测数据及2013年4月至5月过氧乙酰硝酸酯(PAN)的在线监测结果,研究了厦门市O3和PAN的时空分布特征,揭示厦门市光化学污染特性及其污染物的传输规律;探讨厦门市的气候条件对光化学反应的影响,比较植物产生的挥发性有机物(VOCS)和厦门市工业排放的VOCS对光化学反应的影响。     

大气光化学烟雾反应机理比较(Ⅱ)HOx和光化学氧化产物的比较

在相同初始和排放条件下,对四种应用较广的光化学烟雾反应机理(CB4-99,RADM2,RACM,SAPRC99)进行了6组方案的比较.比较物种包括(1)OH和HO2自由基;(2)H2O2,HNO3,PAN,甲醛和有机硝酸酯等光化学产物;(3)甲苯和SO2;(4)NOy,NOa和NOz.由于各机理对VOCs、自由基及含氮化合物处理的不同,导致了模拟结果存在较大差异.我们用模式模拟这些物种时,应特别注意机理不同而带来的模拟结果差异.     

Suwannee河黄腐酸光化学生成溶解无机碳的研究

用模拟太阳光照射Suwannee河黄腐酸以模拟光氧化过程,研究了溶解氧浓度、模拟太阳光波长范围和铁浓度对溶解无机碳产量的影响.结果表明,氧气饱和样品的溶解无机碳生成速率比空气饱和条件下(3.32 μmol/(L·h))增加了40.1%(以照射过程中线性回归的生成速率计算); 实验以Mylar-D、有机玻璃UF-3和有机玻璃UF-4为滤光片研究了波长范围对溶解无机碳产量的影响,近似计算的结果表明UV-B、UV-A 和可见光部分分别占全波段模拟太阳光光化学生成无机碳产量的43%、42% 和 15%; 当样品铁浓度达到10 μmol/L时,其溶解无机碳的生成速率约为初始样品(Suwannee河黄腐酸铁浓度为1.90 μmol/L)的2.8倍,证实了铁在光化学氧化过程中的催化作用.     

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.