两种有机酸存在下铜对中华圆田螺肝脏的氧化应激效应

为探讨不同水平EDTA和柠檬酸(CA)作用下沉积物中铜对底栖无脊椎动物生态毒理学效应,以中华圆田螺为受试生物,研究了肝脏中活性氧(ROS)、丙二醛(MDA)含量、超氧化物歧化酶(SOD)以及过氧化氢酶(CAT)活性的变化规律。研究结果表明:有机酸存在下,铜污染底泥可诱导中华圆田螺肝脏产生ROS。电子顺磁共振(EPR)技术得出的3组双重峰分裂谱线为典型的α-苯基-N-叔丁基甲亚胺-N-氧化物(PBN)捕获羟自由基(·OH)形成PBN/·OH的EPR波谱。有机酸存在下,低剂量铜(≤100 mg·kg-1)对MDA产量影响不显著。较高剂量铜暴露下,EDTA的存在抑制MDA产生,CA的添加则均使MDA含量增加。EDTA存在下铜可显著抑制中华圆田螺肝脏中SOD和CAT活性。相对而言,CA的加入可减缓高剂量铜暴露下中华圆田螺肝脏SOD与CAT酶活性的剧烈变化。     

电化学法生成Fenton试剂及其在工业染料废水降解脱色中的应用

以多孔石墨电极为阴极 ,电解时在阴极通以氧气或空气 ,电解生成的过氧化氢与阳极溶解的Fe2 +进行随后化学反应 ,现场生成羟基自由基 (Fenton试剂 ) ,进而对有机染整工业废水进行降解脱色反应。以可见光吸收谱图表征了工业染料废水经电解槽处理后吸光度的变化 ,以重铬酸钾法测试染料处理后的COD。实验结果表明 ,COD的去除率大于 80 % ,染料的脱色率达 1 0 0 % ,若将电解电流密度控制在 1 0mA/cm2 以下 ,槽电压可控制在 5V以内。实验结果表明 ,向阴极多孔石墨电极中通入空气与通入氧气的效果一致。     

溶液pH及电流浓度对电化学法生成羟基自由基降解机制的影响

用电化学稳态极化曲线分析方法讨论了溶液pH值及电流浓度对染料降解脱色的影响.实验结果表明,pH值将影响着阴极反应的方向、电极电位与染料降解脱色的效果.在酸性溶液中有利于过氧化氢的生成,阴极电位较低,但不利于随后的絮凝步骤;在中性溶液中染料降解脱色的综合效果较好,COD_Cr去除率可达80%以上.文中还讨论了电流浓度对降解脱色效果的影响,当电解槽内电流浓度达0.5 A/L时可取得满意的效果,电流浓度太大时,体系将伴随着析出氢气等的副反应,降解反应的电流效率下降.      

Fenton催化氧化降解藻毒素MCLR的效能研究

研究了Fenton试剂对饮用水中藻毒素MCLR的降解效能,考察了H2O2用量、Fe2+H2O2最佳摩尔比、pH值和反应时间对Fenton降解藻毒素的影响,得到Fenton降解藻毒素的最佳反应条件:H2O2浓度为0.24mol·L-1、Fe2+H2O2摩尔比1∶9、初始pH值为2～3.5、反应时间为45min.同时采用邻二氮菲Fe(Ⅱ)光度法检测Fenton反应中生成的羟基自由基,从而很好地阐明了Fenton催化氧化降解藻毒素的强氧化作用机制.高效液相色谱分析发现,作用机制可能是Fenton催化氧化藻毒素,生成某种相对稳定的中间产物,然后异构化Adda基团的共轭双键,使Adda基团的结构发生变化,从而降低其毒性.     

Comparison of UV/PDS and UV/H2O2 processes for the degradation of atenolol in water

UV/H2O2 and UV/peroxodisulfate (PDS) processes were adopted to degrade a typical β-blocker atenolol (ATL). The degradation efficiencies under various operational parameters (oxidant dosage, pH, HCO3-, humic acid (HA), NO3- , and Cl-) were compared. Principal factor analysis was also performed with a statistical method for the two processes. It was found that increasing the specific dosage of the two peroxides ([peroxide]0/[ATL]0 ) ranging from 1:1 to 8:1 led to a faster degradation rate but also higher peroxide residual. Within the pH range 3-11, the optimum pH was 7 for the UV/PDS process and elevating pH benefitted the UV/H 2O2 process. The presence of HCO3- , HA, and Cl adversely affected ATL oxidation in both processes. The NO3- concentration 1-3 mmol/L accelerated the destruction of ATL by the UV/PDS process, but further increase of NO3- concentration retarded the degradation process, contrary to the case in the UV/H2O2 process. The rank orders of effects caused by the six operational parameters were pH ≈ specific dosage > [HA]0 > [NO3-]0 > [HCO3-]0 > [Cl-]0 for the UV/H2O2 process and specific dosage > pH > [HA]0 > [NO3-]0 > [HCO3-]0 >[Cl-]0 for the UV/PDS process. The UV/PDS process was more sensitive to changes in operational parameters than the UV/H2O2 process but more efficient in ATL removal under the same conditions.     

不同污染区巨菌草生物炭内源污染物分布及其生物毒性

由于生物质原料来源广泛,缺乏生物炭内源污染物及其用量限制标准,极有可能将含有高内源污染物的生物炭用于环境修复,产生潜在的环境风险.采用清洁区、中度和重度污染区的巨菌草为原料制备生物炭,考察其内源铜（Cu）和镉（Cd）全量及其酸溶态含量和持久性自由基（PFRs）分布,并研究生物炭浸出液对小麦根伸长抑制率和抗氧化酶活性的影响.结果表明,重度污染区九牛生物炭Cu和中度污染区水泉生物炭中Cd含量分别是清洁区红壤生物炭Cu和Cd的3.73倍和4.43倍,九牛生物炭中酸溶态Cu含量分别是水泉和红壤生物炭的3.32倍和2.84倍,水泉和九牛生物炭中酸溶态Cd含量分别是红壤生物炭的7.95倍和5.11倍.3种生物炭中均含有相邻氧原子以碳为中心的PFRs,表现为：红壤>九牛>水泉.3种生物炭浸出液对小麦根伸长均表现为抑制作用,但均不同程度地提高了小麦幼苗超氧化物歧化酶（SOD）、过氧化物酶（POD）和过氧化氢酶（CAT）活性,其中九牛生物炭浸出液对小麦根伸长抑制率最高,达到27.7%.本研究表明,生物炭中内源重金属及PFRs等污染物的共同作用对小麦幼苗产生了显著的生物毒性,后期的研究需关注生物炭内源污染物的潜在环境风险,避免产生二次污染等环境问题.     

A critical review on the application of biochar in environmental pollution remediation: Role of persistent free radicals (PFRs)

Biochar as an emerging carbonaceous material has exhibited a great potential in environmental application for its perfect adsorption ability. However, there are abundant persistent free radicals (PFRs) in biochar, so the direct and indirect PFRs-mediated removal of organic and inorganic contaminants by biochar was widely reported. In order to comprehend deeply the formation of PFRs in biochar and their interactions with contaminants, this paper reviews the formation mechanisms of PFRs in biochar and the PFRs-mediated environmental applications of biochar in recent years. Finally, future challenges in this field are also proposed. This review provides a more comprehensive understanding on the emerging applications of biochar from the viewpoint of the catalytic role of PFRs.     

Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO₂ using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO₂ and O₂. The mechanism results show that the pathway of H-abstraction by NO₂ to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO₂ is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216−298 K. The total rate constant of the OTA-NO₂ reaction is 9.9 × 10⁻¹² cm³/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO₂, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO₂ reaction in some polluted areas of China are 35 times longer than those of the OTA-O₂ reaction. In the atmosphere, the NO₂- and O₂- initiated reactions of OTAs have the same ability to form cresols as [NO₂] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO₂]/[O₂] should be controlled to be less than 7.8 × 10⁻⁵ to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO₂ under the atmospheric environment.     

不同源胡敏酸对磺胺嘧啶紫外光降解的影响及作用机制

研究了紫外光照条件下不同来源的胡敏酸（HA）,包括标准品胡敏酸（SPHA）、水稻土胡敏酸（SDHA）、泥炭土胡敏酸（NTHA）和落叶覆盖地胡敏酸（LYHA）对抗生素磺胺嘧啶（SDZ）光降解的影响以及主要活性物种对其光降解效能的贡献.结果表明：SDZ在纯水中及与HA共存条件下,其光降解过程均符合一级动力学模型,且HA对SDZ的光降解具有促进作用,其促进效果从大到小为SPHA > SDHA > NTHA > LYHA.通过羟基自由基（·OH）和单线态氧（¹O₂）淬灭实验发现,不同来源HA产生·OH和¹O₂的能力具有一定差异性.同等背景条件下,SPHA产生的·OH量相对较多,其对SDZ光降解的贡献率（26.97%）最大,而LYHA贡献相对较小（9.33%）.同时,¹O₂对SDZ光降解起主导作用,其降解贡献率为41.33%~51.95%.     

操作条件对电氧化去除废水中有机污染物的影响研究

为优化电催化氧化操作条件、降低能耗,考察了电解温度、直流电源电流密度、方波脉冲电源频率、占空比等工艺控制参数对苯酚模拟有机废水COD去除率的影响。同时,以水杨酸为羟基自由基(·OH)捕捉剂,通过高效液相色谱分析技术对不同电氧化操作条件下·OH的生成量进行间接检测。结果发现,苯酚溶液的COD去除率随电解温度的升高而下降,随电流密度的增大而升高;随着脉冲频率与占空比的增加,苯酚溶液COD去除率均呈现先升高后下降的规律,在脉冲频率为500Hz、占空比为50%时达到最高。操作条件对·OH生成量的影响与其对苯酚溶液COD去除率的影响规律一致,表明操作条件通过影响生成及进入到电解体系中的·OH量从而影响电氧化效率。比较发现,脉冲电源的单位COD处理能耗相比直流电源降低44%,具有明显节能效果。