紫外活化甲酸产二氧化碳阴离子自由基还原Cr (VI)的研究

研究高效还原技术是去除废水中Cr（VI）的有效手段,本研究提出了一种新颖有前景的基于紫外（UV）活化甲酸（HCOOH）产还原性二氧化碳阴离子自由基（CO₂^•;-）去除Cr（VI）的方法.通过对比UV、HCOOH、UV/HCOOH三种体系对Cr（VI）还原效率和电子自旋共振（EPR）对体系中自由基的检测研究了其活化原理和还原机制.结果表明UV能显著活化HCOOH产生CO₂^•-（α_H=19.08G,α_N=15.86G,g=2.0036）.此外,试验考察了主要影响因素对Cr（VI）去除效果的影响,包括初始Cr（VI）浓度、甲酸投加量、初始pH值、反应温度、有机污染物以及水中常见阴离子.结果显示当甲酸浓度为40mmol/L,Cr（VI）初始浓度为10mg/L,反应时间在60min内,UV/HCOOH体系对Cr（VI）的去除率能达到100%.在酸性条件下（pH≤3.5）能显著促进Cr（VI）的还原,且Cr（VI）去除效率随着初始HCOOH浓度和反应温度升高而增加.进一步研究表明,该体系下NO₃^-对Cr（VI）的还原有着显著的促进作用,而Cl^-、HCO₃^-和对硝基苯酚（pNP）则有抑制作用.不同温度下Cr（VI）去除率与时间关系的拟合结果表明,当反应时间t³;40min,UV/HCOOH体系去除Cr（VI）过程遵循准一级反应动力学,根据不同温度下对应的反应速率常数k,结合阿伦尼乌斯方程,计算求得准一级反应的活化能为15.9kJ/mol.     

染色残液电化学处理碳素阴极材料性能比较

为实现染色残液的高效处理及废水回用,鉴于染色残液良好的导电性,选用电化学处理技术,以模拟活性红X-3B染色残液为研究对象,在钌铱形稳电极为阳极和合适的电解条件下,比较石墨板、石墨毡、炭毡、ACF（活性炭纤维毡）、碳纤维电极〔CFF（碳纤维布）、CFB（碳纤维刷）〕等碳素阴极材料的电化学处理效能.结果表明:碳素阴极材料可实现染色残液的完全脱色,活性红X-3B的降解过程符合一级反应动力学特征,其中CFF为阴极时COD_Cr去除率达到86.37%,一级动力学反应常数为0.010 3 min-1,是石墨毡（0.007 3 min-1）的1.4倍.相比于石墨板电极,CFB显示出优异的二电子氧还原和产H₂O₂能力,单位面积产H₂O₂的浓度为10.40 μmol/L,是石墨板（1.08 μmol/L）的9.7倍,产生的H₂O₂导致活性红X-3B的降解,30 min内实现完全脱色.循环伏安曲线表明,碳纤维电极（包括CFF和CFB）的析氧电位明显高于其他电极,可有效抑制析氧副反应,提高有机污染物降解过程中的电催化效率,有利于降低能耗.研究显示,碳纤维可作为阴极材料应用于电化学处理染色残液,具有良好的稳定性.      

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon(SOC) in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O_3 concentrations(daily peak 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/(C·m~3). Diurnal variations of SOC concentration and SOC/organic carbon(OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with O_x(= O_3+ NO_2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon(EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

Fe2+和零价铁活化过一硫酸盐降解酸性橙7

采用环境友好的Fe~(2+)和零价铁(ZVI)作活化剂,活化过一硫酸盐(PMS)来降解水中酸性橙7(AO7).结果表明,在Fe~(2+)-PMS体系中,AO7的降解效果不佳,但通过添加适量的络合剂,AO7的去除率会大幅提高.ZVI在PMS存在下被腐蚀,并能够缓慢、持续不断地释放Fe~(2+).ZVI-PMS体系可以在比较宽泛的pH范围(3～9)有效、快速地降解AO7,并且在酸性条件下降解速率较快.淬灭实验结果显示,硫酸根自由基(SO_4~(·-))对AO7的降解起主要作用.除了Cl~-和高浓度(50 mmol·L~(-1))的NO_3~-能够促进AO7的降解外,其他水中共存的阴离子对AO7在ZVI-PMS体系中的降解具有抑制作用,而腐殖酸(HA)则无明显影响.AO7在超纯水中的去除率高于其他实际水体,但反应90 min后,污水厂出水过滤水和胶体浓缩液中的AO7去除率也可高达98.6%和87.6%,说明ZVI-PMS可能可以有效地去除含有较高DOC含量的污水中的AO7.利用GC-MS检测到辐照后溶液中有3种中间产物,推测主要是通过AO7偶氮键断键后的中间产物进一步氧化形成.此外,TOC在一定程度上降低,说明部分AO7被矿化.     

丰枯水期鄱阳湖表层水中羟基自由基浓度及其抗生素净化作用研究

鄱阳湖位于我国农业大省江西省,表层湖水中羟基自由基(HO·)引发的水体光化学反应,可能对流域内的农业污染物—抗生素具有潜在的净化作用.因此,本研究以氙灯模拟太阳光测得鄱阳湖及周边河流羟基自由基表观光量子产率(ΦHO·),在丰水期为(0.57~10.33)×10~(-5),枯水期为(0.45~3.52)×10~(-5).丰水期溶解态有机物(DOM)对HO·形成的贡献率为85.8%~98.7%,枯水期为58.5%~97.6%,表明DOM是HO·形成的主导物质.可能由于水体混合均匀,丰水期除抚河水体可能有其特殊的化学组成外,其它湖泊与河流的水化学组成接近,表现出随溶解态有机碳含量升高,ΦHO·呈先增大后减小的现象.枯水期水体各化学组成含量显著高于丰水期,光屏蔽与淬灭可能起主要作用,只有当NO_2~-含量较高时才显示出对HO·形成的贡献.依据太阳光强可得鄱阳湖丰水期及枯水期表层水HO·的稳态浓度分别为9.51×10~(-16)与4.92×10~(-17)mol·L~(-1),湖水中5种抗生素在HO·作用下的半衰期分别为2.3~13.9 d与44.5~268.7 d,丰水期鄱阳湖表现出更高的光化学净化能力.     

多核yolk?shell型Co3O4@mSiO2纳米反应器降解双酚A

采用阳离子表面活性剂协助的自模板法合成了中空介孔SiO₂微球（HMSS）,然后向含HMSS的悬浮液中加入醋酸钴溶液和氨水,让两种溶液经HMSS表面介孔进入空腔中反应生成Co₃O₄内核,合成了多核yolk-shell型Co₃O₄@mSiO₂（介孔SiO₂）纳米反应器.结合XRD、XPS、SEM、STEM、BET等手段,分析了纳米反应器的形貌、结构、元素形态和比表面积.结果显示纳米反应器均匀分散,粒径约为300nm,表面布满介孔,内部分布大量Co₃O₄纳米粒子,拥有极大的比表面积161m²/g,远大于Co₃O₄纳米粒子的比表面积35m²/g,能有效吸附双酚A（BPA）,1h吸附容量达12.7mg/g.多核yolk-shell型Co₃O₄@mSiO₂纳米反应器能高效催化过一硫酸氢盐（PMS）降解BPA,2h降解率达81.8%,远高于Co₃O₄纳米粒子的降解率51.3%,同时能节省PMS的投加量,避免水中盐度过高.此外,合成的纳米反应器具有很好的再利用性,在pH值3~9范围内表现出稳定而高效的催化性能.     

影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.     

游离氨对城市生活垃圾渗滤液短程硝化的影响

为了考察游离氨(free ammonia,FA)对高氮城市生活垃圾渗滤液短程硝化的影响,采用“两级UASB-缺氧-好氧系统”处理实际城市生活垃圾渗滤液.首先在UASB1中实现同时反硝化与产甲烷反应,COD在UASB2中进一步去除,在A/O反应器中利用残余COD进行反硝化以及将NH⁺₄-N彻底硝化.试验共进行79 d,经历3个阶段,即稳定短程硝化(40 d)、短程硝化破坏(19 d)、短程硝化恢复(20 d).结果表明,适当的游离氨浓度（40～70 mg·L^-1）可实现稳定的短程硝化,如在阶段1中亚硝态氮积累率为97%,氨氮的去除率为99%.但游离氨浓度在160 mg·L^-1左右会抑制全部的硝化反应.在阶段3中,通过稀释原水降低了游离氨浓度,在短时间内就恢复了短程硝化.可见,游离氨是实现和维持城市生活垃圾渗滤液短程硝化的重要影响因素.     

Evaluating the e ects of granular and membrane filtrations on chlorine demand in drinking water

In this study, chlorine decay experiments were conducted for the raw water from Nakdong River that is treated by Chilseo Water Treatment Plant (CWTP) situated in Haman, Korea as well as the e uents from sand and granular activated carbon (GAC) filters of CWTP and fitted using a chlorine decay model. The model estimated the fast and slow reacting nitrogenous as well as organic/inorganic compounds that were present in the water. It was found that the chlorine demand due to fast and slow reacting (FRA and SRA) organic/inorganic substances was not reduced significantly by sand as well as GAC filters. However, the treated e uents from those filters contained FRA and SRA that are less reactive and had small reaction rate constants. For the e uents from microfiltration, ultrafiltration, and nanofiltration the chlorine demand because FRA and SRA were further reduced but the reaction rate constants were larger compared to those of sand and GAC filter e uents. This has implications in the formation of disinfection by products (DBPs). If DBPs are assumed to form due to the interactions between chlorine and SRA, then it is possible that the DBP formation potential in the e uents from membrane filtrations could be higher than that in the e uents from granular media filters.