Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

• Light irradiation increased the concentration of free radicals on HS. • The increased spin densities on HS readily returned back to the original value. • The “unstable” free radicals induced the formation of reactive radical species. • Reactive radicals’ concentration correlated strongly with EPFRs’ concentration. Environmentally persistent free radicals (EPFRs) in humic substances play an essential role in soil geochemical processes. Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments; however, the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear. In this study, humic acid, fulvic acid, and humin were extracted from peat soil and then in situ irradiated using simulated sunlight. Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time, the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau. After irradiation for 2h, the maximum spin density levels were up to 1.63 × 10¹⁷, 2.06 × 10¹⁷, and 1.77 × 10¹⁷ spins/g for the humic acid, fulvic acid, and humin, respectively. And the superoxide radicals increased to 1.05 × 10¹⁴–1.46 × 10¹⁴ spins/g while the alkyl radicals increased to 0.47 × 10¹⁴–1.76 × 10¹⁴ spins/g. The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions. Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species (R² = 0.65–0.98, p<0.05), which suggested that the newly produced EPFRs contributed to the formation of reactive radical species. Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.     

O3氧化法和O3-H2O2氧化法去除水中聚丙烯酰胺

采用O3氧化法和O3-H2O2氧化法去除水中的聚丙烯酰胺（PAM）,分别考察了反应时间、O3质量浓度、n（H2O2）∶n（O3）和溶液pH对PAM去除效果的影响。实验结果表明：O3氧化的最佳操作条件为反应时间30 min、O3质量浓度22.6 mg/L、溶液pH 8.5,O3-H2O2氧化的最佳操作条件为反应时间10 min、O3质量浓度22.6 mg/L、n（H2O2）∶n（O3）=0.1、溶液pH 8.5;在最佳操作条件下,O3氧化和O3-H2O2氧化均可有效降低PAM溶液的黏度和PAM质量浓度,但对COD的去除效果不佳,黏度可降至和蒸馏水相近,PAM的去除率可达80%以上,而COD的去除率分别约为15%和28%;O3-H2O2氧化后的PAM比O3氧化后的PAM更容易被微生物利用,两种氧化预处理方法均有利于后续的生化处理。     

Phenolic content,antioxidant and antibacterial activity of selected natural sweeteners available on the Polish market

Seventeen natural sweeteners available on the Polish market were screened for total phenolic content, by the Folin-Ciocalteu method, and for antioxidant activity, using the ferric reducing antioxidant power (FRAP) assay and the 2,2′-Azinobis (3-ethylbenzthiazoline-6-sulphonic acid) radical cation decolorization assay (ABTS^·+). In addition, we analyzed antibacterial activities against Staphylococcus aureus strains: both those susceptible and those resistant to methicillin (MRSA). The results of the study showed that total phenolic content, antioxidant activity and antibacterial activity differ widely among different samples of sweeteners. Phenolic content, expressed as a gallic acid equivalent, ranged from 0 mg kg^?1 in white, refined sugar, xylitol and wheat malt syrup to 11.4 g kg^?1 in sugarcane molasses. Antioxidant activity was lowest in refined white sugar, xylitol, brown beet sugar, liquid fructose, and rape honey; it was average in spelt syrup and corn syrup, and highest in sugar cane, beet molasses, date and barley syrups. Despite the great variety of sweeteners, a strong correlation was noted between the concentration of phenolics and antioxidant properties, as determined by the ABTS^·+ method (r = 0.97) and the FRAP assay (r = 0.77). The strongest antibacterial activity was observed in sugarcane molasses, which was lethal to S. aureus strains at 2 and 4% concentrations in medium for susceptible and MRSA strains respectively. Other sweeteners kill bacteria in 6–15% solutions, whereas some did not show any antibacterial activities against S. aureus strains, even at 20% concentrations. Due to their high antioxidant and antibacterial activities, some of the tested sweeteners have potential therapeutic value as supporting agents in antibiotic therapy.     

Fe(Ⅲ)-酒石酸盐配合物体系的光解特性

以Fe(Ⅲ)-酒石酸配合物体系光化学过程中产生的Fe(Ⅱ)和.OH为主要检测对象,探讨了Fe(Ⅲ)-酒石酸配合物体系光化学反应的基本规律及影响因素。结果表明,体系的光化学过程能产生Fe(Ⅱ)和.OH;产生Fe(Ⅱ)的速率远高于产生.OH的速率;Fe(Ⅱ)生成浓度在pH 3.50时最大,.OH则在pH 3.00时最大;配合物的光化学过程中会伴随pH的升高;在照度为3.6×103Lux的日光灯照射下,Fe(Ⅲ)-酒石酸盐配合物初级光解的速率常数为2.1×10-3S-1;Fe(Ⅱ)是高价重金属的主要还原剂,.OH是有机物的主要氧化剂。     

Fe(Ⅲ)/丙酮酸钠体系光解过程中生成的 Fe(Ⅱ)浓度和·OH的浓度变化

以日光灯和金属卤化物灯为主要光源,以Fe(Ⅲ)/丙酮酸钠体系光化学过程中产生的Fe(Ⅱ)和·OH为主要检测对象,探讨了Fe(Ⅲ)/丙酮酸钠体系光解过程中生成的Fe(Ⅱ)和·OH的浓度变化.结果表明,Fe(Ⅲ)/丙酮酸钠体系的光解过程不仅能产生Fe(Ⅱ)和·OH;在丙酮酸钠过量的情况下,光解过程还存在着Fe(Ⅲ)/Fe (Ⅱ)的循环;Fe(Ⅱ)浓度和·OH累积浓度均在pH 3.00时最大;体系的光化学过程中会伴随pH的升高;初始Fe(Ⅲ)浓度和初始丙酮酸钠浓度的提高都有利于Fe(Ⅱ)浓度和·OH累积浓度的提高.     

Si-FeOOH催化臭氧氧化法降解苯胺

通过掺杂Si提高FeOOH的机械强度,制备无定型Si-FeOOH,并用于催化臭氧氧化降解苯胺。考察了n(Si)∶n(Fe)、Si-FeOOH加入量、溶液p H、初始苯胺质量浓度等因素对苯胺去除率的影响,并研究了SiFeOOH的重复利用效果与铁离子的溶出情况。实验结果表明:Si-FeOOH对臭氧氧化降解苯胺具有明显的催化作用,Si-FeOOH催化臭氧氧化对苯胺的降解效果明显高于单独臭氧氧化和FeOOH催化臭氧氧化;在溶液p H为11、Si-FeOOH加入量为1.0 g/L、n(Si)∶n(Fe)=0.55的最佳降解条件下处理初始苯胺质量浓度为300 mg/L的苯胺溶液,降解10 min后,苯胺去除率可达100%;Si-FeOOH催化剂经5次重复使用后,苯胺的去除率仍高达97.8%,且铁离子的溶出量明显低于FeOOH。     

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。     

新型二氧化铅电极处理硝基苯废水

采用高压塑片的方法制备了一种PbO₂电极,用X衍射、扫描电镜、火焰原子吸收分光光度法对该电极性能进行了考察,并探讨了该电极降解硝基苯的机理和工艺条件.结果表明,该电极与普通石墨电极相比,COD_Cr去除率更高,电解5 h COD_Cr去除率最高可达65%.由于PbO₂电极具有较高的析氧电位,在阳极极化下,PbO₂电极表面易生成·OH,这是其电解效率高的主要原因.该电极电解硝基苯的最适条件:ρ(硝基苯)为501.5 mg/L,电极间距为3 cm,溶液pH为7.利用该电极处理含磷酸盐和氯离子的硝基苯废水效果尤为突出,但由于阴极的还原作用,电解过程中硝基苯不能被完全氧化.      

电极喷嘴布置对NO电晕氧化过程影响的试验研究

使用湿空气作为自由基源物质 ,研究了电极喷嘴布置对电晕放电特性、NO电晕氧化过程的影响 .结果表明 ,随着电极喷嘴数的增加 ,总电晕区域变大 ,流光的脉动重复率增加 ,NO的氧化率提高 .试验条件下 ,对应B(14 )、B(8)、A(7)、A(4 )的放电电极 ,电晕反应器NO的氧化率最高可分别达到 65 3 %、5 0 5 %、5 1 3 %、2 7 5 % .采用喷嘴数较多的电极时 ,NO电晕氧化的能量效率较高 ,有效工作区内 ,对应B(14 )、B(8)、A(7)、A(4 )的放电电极 ,电晕反应器NO氧化的能量效率最高分别为 5 3 1g·kWh- 1 、5 0 2g·kWh- 1 、5 0 7g·kWh- 1 、3 8 0g·kWh- 1 ,它们对应的NO氧化率分别为 5 3 8%、42 5 %、48 8%、2 3 0 % .喷嘴数目相同时 ,A型电极所形成的电晕流光在电晕反应器内具有更好的充满度 ,更有利于烟气NOx 脱除 .     

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.