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.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

The Effect of Hydroxyl Radical Generation on Free-Radical Activation of TMP Fibers

The purpose of this work was to study the mechanisms involved in free radical activation of thermal mechanical pulp (TMP) fibers with the ultimate goal of developing methods for bonding wood fiber without the use of traditional adhesives. The generation of hydroxyl radicals in a mediated Fenton system was studied using electron spin resonance (ESR) spin-trapping techniques and indirectly through chemiluminescence measurement. The activation of TMP fibers was also evaluated by ESR measurement of free phenoxy radical generation on solid fibers. The results indicate that low molecular weight chelators can improve Fenton reactions, thus in turn stimulating the free radical activation of TMP fibers. However, it was also shown that excessive and prolonged free radical treatment may cause the destruction of fiber phenoxy radicals. In conclusion, this study demonstrates the potential for application, but also the complexity of free radical chemistry in biological materials, especially with regard to the chelation of transition metals and the interaction between free radicals.     

游离羟基及表面活性剂对乙草胺光解的影响

以高压汞灯为光源,以p-亚硝基-N,N-二甲基苯胺(PNDA)作为·OH自由基的探针,研究了H2O2及表面活性剂0206-B(苯乙烯苯酚聚氧乙烯醚和十二烷基苯磺酸钙混剂)对除草剂乙草胺在水中间接光解作用的影响.结果表明,H2O2对水中乙草胺具有光敏化降解作用,其敏化作用效应与·OH有关;而0206-B对乙草胺具有光猝灭降解作用,光猝灭降解作用效应与0206-B减少水溶液中的·OH自由基含量有关.乙草胺直接光解与H2O2作用的乙草胺间接光解相同的产物有Rf(比移值)为0.12、0.52、0.61、0.72的化合物;H2O2敏化降解抑制了乙草胺直接光解产物Rf为0.04、0.10、0.18、0.21、0.79的化合物产生,但促进乙草胺间接光解Rf为0.45、0.66的新光解产物生成.     

吸烟气相物质引起的脂质过氧化的研究

本文用吸烟气相物质作用于卵磷脂形成的脂质体及人多形核白细胞,用TBA法和共轭二烯法检测吸烟气相物质作用下的脂质过氧化水平,结果发现,随着吸烟气相物质作用时间的延长,MDA和共轭二烯的含量也随之增大。表明吸烟气相物质能够引起脂质过氧化反应。     

二价铁活化过硫酸盐降解土壤中十溴联苯醚

研究了Fe2+活化过硫酸钠产生的硫酸根自由基降解土壤中十溴联苯醚（PBDE-209）的效果,分别考察了Na2S2O8的用量、初始pH值、Na2S2O8与Fe2+摩尔比例、反应时间4个因素对降解效果的影响。通过正交实验确定了降解污染物的最优条件。结果表明,在Na2S2O8用量为0.8 mmol·kg-1,初始pH为5,Na2S2O8与Fe2+摩尔比为2：1,反应时间为30 min的最优条件下,降解率达96.36%。分子探针竞争实验表明体系中产生了硫酸根自由基。Fe2+活化过硫酸钠降解PBDE-209反应过程符合一级反应动力学。