磁性氮掺石墨烯活化过硫酸钾降解水中亚甲基蓝

活化过硫酸盐产生硫酸根自由基的高级氧化技术在水环境污染物治理中引起了广泛的关注和研究.本研究采用水热法制备磁性氮掺石墨烯(M-N-G)作为催化剂.利用SEM、BET、XRD和VSM等手段表征材料,系统研究了该材料活化过硫酸盐降解亚甲基蓝的效能.结果表明:M-N-G的比表面积为94.35 m2·g-1,磁性Fe3O4分布在材料表面,能有效的活化过硫酸钾降解亚甲基蓝.当催化剂的用量为200 mg·L~(-1),过硫酸钾浓度为0.4~0.5 mmol·L~(-1)时,在p H=3~6时对10 mg·L~(-1)亚甲基蓝的降解率达90%以上.体系温度在15~32℃时,降解速率常数在0.0227~0.0488 min-1,反应活化能为33.7 k J·mol-1.EPR分析及自由基漼灭实验证明了体系中有羟基自由基和硫酸根自由基产生.TOC分析结果表明:TOC去除率可达50%.M-N-G经过简单的稀硫酸和水洗后,可高效重复利用4次.该技术方法简单、高效、无二次污染,能为有机污染物废水处理提供一种新的方法选择.     

栘依树抗氧化剂对香烟烟气自由基及人淋巴细胞姐妹染色单体交换率的影响

采用电子顺磁共振法研究了栘依树抗氧化剂对香烟烟气自由基含量的影响,并比较了不同自由基含量的香烟烟气冷凝物(CSC)对人淋巴细胞姐妹染色单体的损伤情况.在香烟滤嘴中注入50μL0.2%的栘依树抗氧化剂溶液后,香烟烟气中气相、粒相自由基含量分别降低40.2%和28.3%,平均降低39.6%;中高剂量的实验烟(添加栘依树),与对照烟(不加栘依树)相比,人淋巴细胞姐妹染色单体交换率显著降低(t＞t0．05),其中中剂量烟降低幅度更大;低剂量实验烟与对照烟相比,姐妹染色单体交换率也有降低趋势,但差异不显著(t相似文献   

大气颗粒物致机体损伤的OH自由基机制

流行病学研究表明可吸入大气颗粒物浓度上升与人群呼吸道和心血管疾病发病率上升密切相关.毒理学实验和人体暴露研究显示可吸入大气颗粒物可导致机体广泛的损伤,但其致毒机制尚未明确.大量体内和体外研究表明了活性氧在颗粒物致毒过程中的重要作用,其中OH自由基具有极高的反应活性,是可吸入颗粒物致毒的重要机制.在总结国内外相关研究基础上,综述了OH自由基可能造成的大分子损伤、大气可吸入颗粒物暴露引发机体产生OH自由基的分子机制以及生物体系中OH自由基的检测手段,并对该领域的研究方向进行了展望.     

Fe(Ⅱ)/K2S2O8对水体中As(Ⅲ)的氧化研究

研究了Fe(Ⅱ)/K2S2O8对水体中As(Ⅲ)的氧化作用,以及pH值、Fe(Ⅱ)初始浓度等因素对氧化As(Ⅲ)的影响,并且采用分子探针法的竞争性实验鉴定了体系中产生的活性中间体,探讨了K2S2O8在Fe(Ⅱ)存在的条件下对As(Ⅲ)的氧化机理。     

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.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

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.     

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.     

羟胺强化Fenton反应降解水中氯酚

针对传统Fenton体系Fe（Ⅲ）累积和pH适用范围过窄等缺点,采用羟胺（HA）强化的HA-Fenton体系,以对氯苯酚（4-CP）为目标污染物进行降解实验,考察了Fe（Ⅱ）投加量、H2O2投加量、HA投加量和溶液pH等工艺条件对4-CP去除率的影响。实验结果表明：HA-Fenton体系适用于酸性和弱酸性条件,最佳pH范围为3.0~4.0;在溶液pH为3.0、Fe（Ⅱ）投加量为5.0 μmol/L、H2O2投加量为0.4 mmol/L、HA投加量为0.20 mmol/L的最适条件下,反应10 min, 4-CP去除率达64.25 %。