苯水相光氧化反应形成二次有机气溶胶的实验研究

来源于机动车尾气的苯能溶于大气水滴、云雾等水相中并发生水相光氧化反应,在水分蒸发后,产物保留在颗粒相中形成二次有机气溶胶(SOA)粒子.本文采用雾化器将羟基启动苯水相光氧化反应溶液雾化产生气溶胶粒子,通过扩散干燥管除去水蒸气后产生SOA粒子,采用气溶胶激光飞行时间质谱仪进行在线检测,利用紫外可见吸收光谱仪、红外光谱仪和液相色谱串联质谱仪离线测量SOA的化学组分.实验结果表明,激光解吸附质谱中存在醛类(m/z=29(CHO~+)、57(CHOCO~+))、羧酸(m/z=44(COO~+))和苯环(m/z=39(C_3H~+_3)、65(C_5H~-_5))特征裂解碎片峰.SOA粒子的红外光谱图中存在苯环C—H和C=C双键,以及C=O双键、C—O、O—H和C—O—C键的伸缩振动吸收峰,电喷雾电离质谱中存在m/z高达915的离子峰.这表明醛类、羧酸、酚类、芳香醚类产物和酚类产物发生聚合形成的高分子量化合物是SOA粒子的主要化学组分.这为研究人为源挥发性有机化合物水相反应形成SOA的机理提供了实验依据.     

水体中亚硝酸盐的光降解

一定浓度的亚硝酸盐溶液经太阳光模拟器照射一定时间后,观测溶液中亚硝酸盐的含量变化.改变溶液条件（介质、pH）和光照条件（时间、光强）等实验条件,同时进行黑暗对照实验,探求影响亚硝酸盐光解的因素和规律.结果表明,在光照的8 h内,时间越长亚硝酸盐的降解率越大,基本符合一级反应动力学曲线;光照强度越大亚硝酸盐的降解程度越大...     

Capillary electrophoresis to analyze water-soluble oligo(hydroxyacids) issued from degraded or biodegraded aliphatic polyesters

In an attempt to increase the range of analytical techniques able to monitor ultimate degradation stages of degradable, biodegradable, and bioresorbable polymers, capillary zone electrophoresis (CZE) was used to analyze tentatively oligomers formed during thermal condensation of lactic, glycolic, anddl-3-hydroxybutyric acids. The influence of the buffer and of capillary coating are discussed in terms of electroosmotic flow. Typical analyses were first performed using a 0.1M borate buffer (pH 8.9) with anodic injection. In the case of lactic acid, seven peaks were well separated, while only three peaks were observed for glycolic acid. A more complex situation was found fordl-3-hydroxybutyric acid oligomers. The first five peaks were split. The major component of each doublet was attributed to hydroxy-terminated oligomers, whereas the satellite peaks were assigned to oligomers bearing a C=C double bond at the noncarboxylic terminus. CZE of pH-sensitive lactic acid oligomers was also performed in 0.05M phosphate buffer (pH 6.8) with cathodic injection after physical coating of the fused-silica capillary with DEAE-Dextran. The buffer-soluble fraction present in lactic acid oligomers was extracted from a dichloromethane solution. Extracts issued from different batches of lactic acid condensates gave a constant water-solubility pattern whose cutoff was at the level of the decamer. CZE was also used to monitor thein vitro aging of aqueous solutions of these water-soluble oligomers. The lactyllactic acid dimer appeared more stable than higher oligomers, thus showing that ultimate stages of the degradation did not proceed at random. These physicochemical characteristics were used to complement the degradation pathway based on diffusion of oligomers duringin vitro aging of large size lactic acid plates made by compression molding. CZE data showed that lactic acid was the only component which was released in the aqueous medium during degradation.Presented by C.B. at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995, Durham, NH, USA.     

合成氨废水资源化处理技术研究进展

合成氨废水具有高氨氮的特点,高氨氮污水的治理是大家关注的焦点。文章介绍处理高氨氮废水的三种资源化回收技术,(1)以氨水形式回收氨氮的废水处理技术;(2)将氨氮制成硫酸铵回收利用的废水治理技术;(3)既能高效脱氮又能充分回收氨氮的磷酸铵镁(俗称鸟粪石)结晶沉淀法,其中重点介绍鸟粪石结晶沉淀法回收氨氮技术。这些废水处理技术有效地治理了高氨氮废水,具有节能减耗、无二次污染和污染物可得到充分回收利用等特点,是处理高浓度氨氮废水的可持续发展方向。     

Effects of low temperature on aluminum(III) hydrolysis: Theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)3(am)) and a distribution diagram of hydrolyzed Al species. First, thermodynamic data of Al species at 4 degrees C were calculated from that at 25 degrees C. A well confirmed polymeric Al species, AlO4Al12(OH)24(7+)(Al13), was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), 27Al nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4 degrees C caused the Al(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)3(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al13, and solid-phase Al(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25 degrees C, Al13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4 degrees C, All3 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)3 over the range of 1.8 pH units at 4 degrees C in comparison with the range of 0.5 pH unit at 25 degrees C.     

圆盘式固相萃取HPLC法测定饮用水中微囊藻毒素LR和RR

采用固相微萃取与高效液相色谱联用技术（SPE／HPLC）测定饮用水的微囊藻毒索,并对SPE的萃取条件和HPLC的色谱条件进行了优化,对SPE的多项参数,诸如萃取率、检出限及测定限以及准确度和精密度均作了测试。通过实际水样进行了分析,该方法测定MC—LR（LR型微囊藻毒索）的线性范围为0．5～50ug／L,相关系数为0．9992;测定MC—RR（RR微囊藻毒索）的线性范围为0．5—50ug/L,相关系数为0．9989。SPE法之优于LLE法主要在于分析过程快速,有机溶剂使用量大大减少,方法更适合于大量水样中有机污染物的现场取样处理。     

锰离子催化臭氧液相烟气脱硫实验研究

对Mn2+催化臭氧(O3)液相氧化脱除二氧化硫(SO2)进行了实验研究,以揭示Mn2+对臭氧液相氧化SO2的影响.采用标准碘量法测定了O3浓度曲线.实验比较了添加Mn2+前后吸收液对SO2的脱除效率,并研究了O3与SO2摩尔比([O3]/[SO2])、Mn2+浓度对SO2脱除效率的影响.在[O3]/[SO2]=0.5、未添加Mn2+时O3对SO2的氧化效率为35%,而添加Mn2+后的氧化效率达到70%.随着[O3]/[SO2]的增大,SO2脱除效率逐渐增加,而且脱除效率也随Mn2+浓度的增加而增加,合适的Mn2+浓度范围为1.2×10-2~1.2×10-1mol/L.     

改变垫水层沸点的薄层扬沸实验研究

扬沸是油池火灾的一种特殊现象,燃料和垫水层交界面的过热温度和沸腾状态是决定扬沸是否发生以及发生时间的最主要因素,过热温度由沸点决定。在垫水层中添加氯化钠能够改变垫水层的沸点,从而改变交界面的过热温度。在垫水层添加氯化钠使其成为饱和氯化钠水溶液,对此条件下的油池火燃烧进行实验探究,以验证前人关于扬沸临界条件的研究结果,并为扬沸防治提供思路。垫水层改变为饱和氯化钠溶液后,柴油实验组均没有发生扬沸,且观察到火焰温度和热辐射强度的下降。表明此方法可以有效抑制扬沸的发生。     

次氯酸钙溶液脱硫脱硝一体化过程热力学分析

烟气脱硫脱硝一体化技术已成为当前大气污染防治领域的研究热点,其中氧化剂液相吸收法极有可能率先实现产业化。文章理论上首次提出了次氯酸钙溶液脱硫脱硝一体化技术,利用热力学函数计算分析了脱硫脱硝反应的方向和限度,通过SO2和NO平衡分压计算推导了污染物的脱除效率,考察标准吉布斯函数变分析了该技术的优势。结果表明:脱硫脱硝反应的标准吉布斯函数变分别为-614.55和-888.21 kJ/mol,热力学角度上完全可行,反应限度极深,优于文献中介绍的尿素、NaClO2、KMnO4/NaOH溶液吸收法和臭氧结合氨水吸收法。同时,SO2和NO平衡分压很小,说明次氯酸钙溶液几乎可以完全脱除烟气中的SO2和NOX。