Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

碳纤维电极上降解有机染料的研究

以碳纤维电极为工作电极,CoSO4为催化剂,利用电生羟基自由基对中性红、罗丹明B、碱性品红等三种有机染料进行降解．研究电解电位、pH值、温度等因素对染料降解脱色的影响．在优化条件下,脱色率大于95％,COD去除率达90％以上．     

稀水溶液中Cr(Ⅵ)光化学还原的研究

研究了稀水溶液中Cr(Ⅵ)的光化学还原过程,考察了·OH自由基俘获剂的种类、结构及溶液pH值对Cr(Ⅵ)还原的影响结果表明稀水溶液中Cr(Ⅵ)的还原过程分化学还原与光化学还原两步进行,前者为直接氧化还原过程,后者则经历自由基反应;·OH自由基俘获剂中羟基的数量和位置对Cr(Ⅵ)的还原均有影响,羟基α位碳上氢原子数量愈多,碳氢键强度愈小,愈有利于Cr(Ⅵ)还原;溶液pH值对Cr(Ⅵ)的还原有重要影响,随着pH值的升高,其还原率和反应速率均下降,当pH≥70时,Cr(Ⅵ)的还原基本停止     

天然水体中亚硝酸根和硝酸根的光化学研究进展

综述了近年来亚硝酸根和硝酸根 (NO-2 /NO-3 )在天然水体中的环境光化学研究进展。重点介绍了NO-2 /NO-3 光解生成活性氧 (如羟基 )的机理及其影响因素 ,探讨了NO-2 /NO-3 光解引发天然水体中有机物反应的环境意义 ,并据此提出了本领域今后的研究方向     

碲化镉量子点诱导氧自由基产生的检测

随着量子点(quantum dots,QDs)在生物标记和医学影像等领域的应用日益广泛,其环境暴露量逐渐增加,深入探讨QDs的毒性机制具有重要意义。QDs通过产生活性氧(ROS)诱发毒性效应是目前普遍接受的毒作用模式。为了探讨量子点的毒性与所诱发的ROS的种类和数量的关系,选用碲化镉量子点(CdTe QDs和CdTe/ZnS QDs),利用电子顺磁共振技术(EPR)分别测定了CdTe QDs和CdTe/ZnS QDs在无细胞体系中诱导ROS产生的种类和强度;利用EPR法、紫外可见分光光度法和荧光分光光度法分别测定了4、20和100nmol·mL-1的CdTe QDs和CdTe/ZnS QDs对超氧阴离子(·O2-)和羟基自由基(·OH)产生的促进作用。实验结果显示,CdTe QDs可诱导·O2-的产生;CdTe QDs和CdTe/ZnS QDs对·OH与·O2-的产生有明显的促进作用,且具有剂量-效应关系。研究表明,量子点可诱导和促进ROS产生,不同结构量子点对ROS的诱导和促进作用不同。     

Simultaneous removal of arsenate and fluoride from water by AI-Fe （hydr）oxides

A1-Fe （hydr）oxides with different A1/Fe molar ratios （4：1, 1：1, 1：4, 0：1） were prepared using a co- precipitation method and were then employed for simultaneous removal of arsenate and fluoride. The 4A1 ： Fe was superior to other adsorbents for removal of arsenate and fluoride in the pH range of 5.0-9.0. The adsorption capacity of the A1-Fe （hydr）oxides for arsenate and fluoride at pH 6.50.3 increased with increasing A1 content in the adsorbents. The linear relationship between the amount of OH released from the adsorbent and the amount of arsenate or fluoride adsorbent by 4A1 ： Fe indicated that the adsorption of arsenate and fluoride by A1- Fe （hydr）oxides was realized primarily through quantita- tive ligand exchange. Moreover, there was a very good correlation between the surface hydroxyl group densities of A1-Fe （hydr）oxides and their adsorption capacities for arsenate or fluoride. The highest adsorption capacity for arsenate and fluoride by 4A1 ： Fe is mainly ascribed to its highest surface hydroxyl group density besides its largest pHpzc. The dosage of adsorbent necessary to remove arsenate and fluoride to meet the drinking water standard was mainly determined by the presence of fluoride since fluoride was generally present in groundwater at much higher concentration than arsenate.     

Effects of cucl2 on UV‐mutagenesis and on DNA damage in a restriction fragment of E. Coli gpt∗

CuCl₂ does not cause Trp⁺ reversion in E. coli WP2. However, when the bacteria are exposed to CuCl₂ and UV‐irradiated, a greater than 3‐fold enhancement of mutagenesis (compared to UV alone) is seen at 30 μMCuCl₂, and significant enhancement is seen even at 3 μM. The mechanism for this comutagenic effect was studied using a restriction fragment of the E. coli gpt gene. Whereas UV or CuCl₂ alone caused few strand breaks, UV + CuCl₂ induced breaks at every site. This reaction was blocked by KI, a free radical scavenger. While UV alone induced alkali‐labile sites, UV+ CuCl₂ induced many more such sites and altered the sequence specificity. We suggest that at least some of the comutagenic effect might be due to hydroxyl radical formed via a Fenton reaction.     

二价铁催化过碳酸钠处理水中乙苯

采用Fe(II)催化过碳酸钠(SPC)体系处理水溶液中的乙苯(EB),考察c(SPC)、c(Fe(II))、阴离子浓度、天然有机物(NOM)以及溶液初始pH值对EB降解效果的影响,并确定EB降解过程中起主导作用的自由基.结果表明,对于浓度为1mmol/L的EB溶液,c(SPC)、c(Fe(II))均为12mmol/L时,20min内EB可被完全去除; Cl^-、HCO₃^-、NOM的存在均会抑制EB降解,SO₄^2-和NO₃^-对EB降解无影响;溶液初始pH值(pH3.00~11.00) 越高,EB去除率越低,但当pH=9时,降解效果仍很显著,表明该体系能够在较宽pH值范围内高效降解水溶液中EB;自由基探针试验证实体系中存在^·OH和O₂^·-,自由基清扫试验表明^·OH对EB降解起主导作用.     

有机污染物在海泡石矿物的界面吸附与降解研究进展

海泡石是一种典型的纤维状富镁硅酸盐粘土矿,广泛地应用于土壤污染治理、空气净化和水体污染物吸附等领域,然而海泡石表面Si-OH反应活性尤其是与有机污染物的反应机制尚未有清楚的认识.本文综述了海泡石对水体环境中有机污染物的界面吸附与降解研究进展,首先介绍了海泡石对有机染料、有机农药、药物和个人护理品等有机污染物的界面吸附情...     

Determination of hydroxyl radicals in TiO2/Ti photoelectrocatalytic oxidation system using Fe(phen)3 2+ spectrophotometry

A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic(PEC)oxidation system was established by o-phenanthroline-Fe(Ⅱ)(Fe(phen)32+) spectrophotometry and using anion exchange membrane. Fe concentration of hydroxyl radicals can be calculated through determining the change of the Fe(phen)33+ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 (isoelectric point), and the change direction of pH after illumination tended to nearby isoelectric point.