Ozone episodes during and after the 2018 Chinese National Day holidays in Guangzhou: Implications for the control of precursor VOCs

The impact of reducing industrial emissions of volatile organic compounds (VOCs) on ozone (O₃) pollution is of wide concern particularly in highly industrialized megacities. In this study, O₃, nitrogen oxides (NOx) and VOCs were measured at an urban site in the Pearl River Delta region during the 2018 Chinese National Day Holidays and two after-holiday periods (one with ozone pollution and another without). O₃ pollution occurred throughout the 7-day holidays even industrial emissions of VOCs were passively reduced due to temporary factory shutdowns, and the toluene to benzene ratios dropped from ∼10 during non-holidays to ∼5 during the holidays. Box model (AtChem2-MCM) simulations with the input of observation data revealed that O₃ formation was all VOC-limited, and alkenes had the highest relative incremental reactivity (RIR) during the holiday and non-holiday O₃ episodes while aromatics had the highest RIR during the non-pollution period. Box model also demonstrated that even aromatics decreased proportionally to levels with near-zero contributions of industrial aromatic solvents, O₃ concentrations would only decrease by less than 20% during the holiday and non-holiday O₃ episodes and ozone pollution in the periods could not be eliminated. The results imply that controlling emissions of industrial aromatic solvents might be not enough to eliminate O₃ pollution in the region, and more attention should be paid to anthropogenic reactive alkenes. Isoprene and formaldehyde were among the top 3 species by RIRs in all the three pollution and non-pollution periods, suggesting substantial contribution to O₃ formation from biogenic VOCs.     

Ba/TiO2/MCM-41光催化降解对硝基苯甲酸

以钛酸丁酯为钛源、MCM-41分子筛为载体,采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Ba/TiO2/MCM-41。结果表明:Ba/TiO2/MCM-41是一种比表面积高达341.2 m2/g的介孔材料,主要晶相为锐钛矿相,比P25有更强的紫外光吸收。将Ba/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L,对硝基苯甲酸初始pH为4、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到96.0%。用紫外光谱、红外光谱和高效液相色谱分析对硝基苯甲酸降解前后的变化,发现随着光照时间延长,苯环上的硝基、羧基吸收峰逐渐减弱;对硝基苯甲酸首先被降解为一些中间小分子产物,随着反应进行,小分子物质也逐渐被降解。     

山东临沂大气夏季典型时段臭氧污染特征及其控制因素分析

2020年6月,在山东省临沂城区开展臭氧（O₃）及其前体物观测实验,基于观测数据结合MCM光化学模式模拟,对6月中旬O₃污染特例生成机理及控制机制进行了分析.结果发现,尽管观测期间降水较多,一旦天气转晴,O₃迅速积累并超标,1-h和8-h φ（O₃）超标天数分别为10 d（频率32%）和14 d（45%）. O₃日变化呈单峰模态,峰值出现在午后16:00. MCM模拟结果表明,光化学污染特例日O₃日均净生成反应速率为20×10^-9 h^-1, HO₂·+NO和RO₂·（除CH₃O₂·外）+NO反应分别贡献O₃生成的49.0%～51.1%和37.3%～40.2%;·OH+NO₂反应对O₃总消耗的贡献约为35.1%～57.4%. VOCs反应活性、增量反应活性RIR和...     

介孔钛硅分子筛的表面化学特征及除铅机制研究

以表面活性剂在水溶液中形成的液晶相为模板剂，考察了钛含量对制备介孔钛硅分子筛性质的影响；应用表面络合反应关系式计算了介孔钛硅分子筛表面络合反应的基本特征参数。研究了溶液ｐＨ值、温度等对Ｐｂ＾２＋离子在介孔钛硅分子筛表面吸附的影响；并就Ｐｂ＾２＋离子在介孔钛硅分子筛表面的吸附动力学、吸附等温线和吸附机理进行了探讨。     

烟雾箱与数值模拟研究苯和乙苯的臭氧生成潜势

结合光化学烟雾箱实验与数值模拟研究了苯和乙苯在NO x存在条件下的光氧化臭氧生成潜势.重复实验表明,在乙苯-NO x反应体系中,反应物初始浓度、温度、湿度和光照强度接近的条件下,整个反应过程中臭氧的最大偏差仅为4%,证明了烟雾箱的可重复性较高.在烟雾箱实验的基础上,使用MCM(master chemical mechanism)模拟了苯和乙苯的光氧化O3生成,并将其结果与实验数据进行了比对分析.干燥(≤5%)时MCM对苯和乙苯的模拟结果与实验结果较接近,如在苯-NO x反应体系中,MCM模拟的O3峰值比实验值偏大20%;在湿度为5%~70%时,MCM模拟的乙苯光氧化O3峰值与实验值偏高约(10%~25%).用MCM模拟了太阳光照条件下苯和乙苯的臭氧生成等值线,得到在它们浓度为(10~50)×10-9,NO x在(10~100)×10-9时,苯和乙苯的6 h臭氧贡献值分别为(3.1~33)×10-9和(2.6~122)×10-9,臭氧峰值范围分别是(3.5~54)×10-9和(3.8~164)×10-9.此外,模拟得到苯和乙苯的最大增量反应活性(maximum incremental reactivity,MIR)值分别为0.25/C和0.97/C(每单位碳).该结果与Carter通过SAPRC机制得到的MIR值趋势一致.模拟得到苯和乙苯的最大臭氧反应活性(maximum ozone reactivity,MOR)分别为0.73/C和1.03/C.苯的MOR值远高于Carter使用SAPRC得到的结果,说明根据Carter得到的苯MOR会低估苯的O3潜势.     

Ba/TiO_2/MCM-41光催化降解对硝基苯甲酸

以钛酸丁酯为钛源、MCM-41分子筛为载体,采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Ba/TiO2/MCM-41。结果表明：Ba/TiO2/MCM-41是一种比表面积高达341.2 m2/g的介孔材料,主要晶相为锐钛矿相,比P25有更强的紫外光吸收。将Ba/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L,对硝基苯甲酸初始pH为4、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到96.0%。用紫外光谱、红外光谱和高效液相色谱分析对硝基苯甲酸降解前后的变化,发现随着光照时间延长,苯环上的硝基、羧基吸收峰逐渐减弱;对硝基苯甲酸首先被降解为一些中间小分子产物,随着反应进行,小分子物质也逐渐被降解。     

MCM高过载环境适应技术的应用和发展

本文探讨了耐高过载概念的基本内涵,阐述了军用MCM耐高过载技术研究的主要内容及其应用情况,介绍了MCM耐高过载技术研究和应用在近期及未来的发展方向。