水稻秸秆生物炭对罗丹明B的吸附与降解

生物炭对污染物的吸附是生物炭环境效应研究的重要环节,而生物炭中的自由基对有机污染物降解行为的影响还没有得到应有的关注。以水稻秸秆为原材料,研究不同热解温度下制备的生物炭对罗丹明B的吸附和降解,通过荧光光谱法分析生物炭-罗丹明B体系反应前后上清液荧光光谱特性的变化来表征其中的降解现象。结果表明,在350℃和500℃生物炭-罗丹明B反应体系中,其上清液荧光光谱明显发生蓝移现象,表明该体系中存在着明显的降解现象。通过对这2个体系反应后生物炭固体颗粒的萃取来对降解作用进行定量分析,降解作用在这2个体系中所占的比例分别为28%和30%。水稻秸秆生物质炭对罗丹明B具有较好的吸附效果,Freundlich方程可以较好地描述水稻秸秆生物质炭对水中罗丹明B的吸附行为,固液比在3：1 000时生物炭最大吸附量为3.33 mg·g-1。这表明在水稻秸秆生物炭-罗丹明B反应体系中,不仅存在吸附作用,还伴随降解作用。     

CuxTi（1-x）O2光催化降解硝基苯的性能及最优铜掺杂工艺

为增强TiO2光催化降解硝基苯的性能,采用溶胶-凝胶方法进行TiO2的铜掺杂改性,并通过性能表征与分析确定最优铜掺杂量。XRD、FESEM与Jade分析得出,所制备的1.0%、1.5%、2.0%和2.5% Cu-TiO2在各项指标优于德国P25-TiO2,晶粒尺寸20~50 nm,其中1.5%摩尔比Cu-TiO2的XRD峰值最高和结晶度最好,且团聚现象较弱,且晶粒尺寸小于P25。结合铜掺杂结构、微应力变化以及对硝基苯的降解性能,采用1.5%摩尔比Cu-TiO2光照180 min对硝基苯降解效率最优,是P25-TiO2降解性能的2倍,且遵循拟一级反应动力学。EDS与降解实验联合得出最优降解硝基苯的铜掺杂TiO2式为Cu0.018 3Ti0.981 7O2。模拟含硝基苯废水中C和N元素浓度的变化规律,显示Cu0.018 3Ti0.981 7O2降解硝基苯存在苯环被矿化生成CO2和NO2-键断裂等反应过程。     

Free radical biology in neurological manifestations: mechanisms to therapeutics interventions

Environmental Science and Pollution Research - Recent advancements and growing attention about free radicals (ROS) and redox signaling enable the scientific fraternity to consider their involvement...     

紫外波长对UV/Cl2高级氧化去除水中有机物的影响

为明确紫外波长对UV/Cl2高级氧化体系的影响,使用中心波长分别为267、275和286 nm的发光二极管LED作为光源,探究Cl2光解动力学、UV/Cl2体系自由基生成、对模式化合物溶液以及天然水、再生水TOC的去除。结果表明：在中性或酸性体系中,267 nm最接近HClO最大吸收波长237 nm,吸光度和量子产率均较大,羟基自由基产生水平较高,有机物去除效果较好;在碱性体系中,286 nm最接近ClO-最大吸收波长292 nm,尽管量子产率较小,但吸光度很大,有机物去除效果较好;由于水杨酸在292 nm附近有较强的竞争吸收,使用UV286去除水杨酸效果被削弱。应用UV/Cl2技术选择波长时需要考虑吸光度、量子产率、竞争吸收等因素;对于弱碱性天然水或再生水,采用波长为292 nm的紫外光一般可获得较优处理效果。     

Potential effects of UV-B on the chemical environment of marine organisms: a review

An increase in ultraviolet-B (UV-B) due to depletion of stratospheric ozone may affect growth of marine phytoplankton by altering the chemistry of their environment. Production of bioactive free radicals, photodecomposition of organic matter, and availability of trace metals are likely to be altered by increased UV-B flux. Such changes to the chemical environment may be both deleterious and beneficial to marine phytoplankton. Extracellular free radicals such as OH, Br(2)(-), and CO(3)(-) are predicted to have a negligible impact, but superoxide and its decomposition product hydrogen peroxide may react rapidly with cell surfaces and destroy membrane function and integrity. Increased UV-B will enhance the bioavailability of the redox active trace metals Fe and Cu. Thus, in the Fe-limited high latitude ocean, increased Fe availability may promote phytoplankton production, while in other parts of the ocean increased Cu availability may be toxic. Overall, the interdependent direct and indirect effects of UV-B on phytoplankton may compensate for each other and account for the ability of marine ecosystems to be subjected to widely variable UV-B flux without apparent damage.     

利用活性氧分子消除污水中的COD

采用强电场电离放电制取高浓度的活性氧分子O2+和O3,这些活性氧分子与污水中水反应生成羟基自由基OH,可快速把污水中COD降解成无害的CO2、H2O,污水中COD浓度从132 mg/L降至22.6mg/L,COD的去除率达到82.9%,达到回用水质量标准(≤ 50 mg/L),该方法有助于解决目前污水回用存在的问题。     

Photochemical formation of hydroxyl radicals catalyzed by montmorillonite

In this work, the photooxidation of benzene and the formation of phenol in aqueous suspensions of the iron-rich montmorillonite under irradiation of a 250W metal halide lamp (lambda> or = 365nm) were investigated. We confirmed that hydroxyl radicals (()OH) were produced by illuminating montmorillonite and was responsible for the photooxidation of benzene in aqueous suspensions of montmorillonite. Low pH value facilitated the formation of hydroxyl radicals in the pH range of 2.0-10.0. The ()OH concentration increased with increasing the concentration of montmorillonite in aqueous solutions in the range of 0-20.0gl(-1). Higher concentration like 25.0gl(-1) montmorillonite inhibited the ()OH production. Iron, predominantly free iron in the clays, is believed to be one of the most important factors determining ()OH formation. Structural irons in montmorillonite have contributions to ()OH formation, especially in the presence of carboxylate ions. The formation of ()OH from montmorillonite under irradiation of near UV and visible light indicates that clays might play important role not only in transfer through adsorption but also in transformation through oxidation of organic compounds on the surface of clay particles in air, water, soil or even top sediments.     

Mn3O4催化臭氧化钻井废水的作用机理

通过静态实验,探讨了Mn3O4对钻井废水臭氧化过程的催化作用机理,考察了Mn3O4及Cl-对臭氧分解、水体湍动程度、羟基自由基抑制剂碳酸氢根和叔丁醇的加入对COD去除率的影响,分析了反应过程中TOC和pH的变化。结果表明,催化剂加量为100 mg/L时,臭氧分解率由单独臭氧时的38.2%增加到81.4%,Mn3O4对钻井废水中有机物的吸附去除率仅为2%,O3/活性炭体系对COD去除率与单独臭氧效果接近,说明臭氧在催化剂表面存在吸附作用,促进臭氧分解;水体不搅拌与搅拌速度增加为900 r/min时,COD去除率由52%增加到58%,搅拌程度对钻井废水COD去除效果影响不大;HCO3-浓度为100 mg/L时,COD去除率降低到41.2%,说明了体系中有羟基自由基产生;氯离子浓度为1 000 mg/L,臭氧的分解率降低了9.2%,证明了臭氧在催化剂表面的吸附作用;羟基自由基抑制剂叔丁醇的加入,使得COD去除率由54.3%降低为40.8%,证实了反应体系中存在羟基自由基。同时在反应过程中,体系的TOC 由191.9 mg/L降低至37.6 mg/L;pH由原来的11.2降低到6.3。实验现象说明,臭氧吸附在Mn3O4催化剂表面,分解产生羟基自由基,进而氧化去除钻井废水中有机物,这在某种程度上证明了Mn3O4催化臭氧化对有机物的降解遵循羟基自由基机理。     

Antioxidant activity and enzyme inhibitory potential of Euphorbia resinifera and E. officinarum honeys from Morocco and plant aqueous extracts

Natural products may be applied in a wide range of domains, from agriculture to food and pharmaceutical industries. In this study, the antioxidant properties and the capacity to inhibit some enzymatic activities of Euphorbia resinifera and Euphorbia officinarum aqueous extracts and honeys were assessed. The physicochemical characteristics were also evaluated. Higher amounts of iron, copper and aluminium were detected in E. officinarum honey, which may indicate environmental pollution around the beehives or inadequate storage of honey samples. This honey sample showed higher amounts of total phenols and better capacity for scavenging superoxide anion free radicals and DPPH free radicals as compared with E. resinifera honey, but poorer capacity for inhibiting lipoxygenase, acetylcholinesterase, tyrosinase and xanthine oxidase. The ratio plant mass:solvent volume (1:100) and extraction time (1 - 2 h) were associated with higher total phenols and better antioxidant activities and lipoxygenase, acetylcholinesterase and tyrosinase inhibitory activities, regardless of the plant species. The aqueous extracts had systematically higher in vitro activities than the respective honey samples.

     

Treatment of phenolic wastewater by horseradish peroxidase immobilized by bioaffinity layering

Horseradish peroxidase was immobilized by bioaffinity layering and used for the treatment of wastewater containing p-chlorophenol. For this purpose, lectin Concanavalin A was bound to Sephadex beads. The glycoenzyme peroxidase was layered upon this Con A layer. Subsequently, alternate layers of the enzyme and Con A were applied. The most efficient design consisted of three layers of Con A and peroxidase each. This immobilized enzyme preparation retained 80% of the activity of the free peroxidase used for immobilization. PEG at the concentration of 0.1 mg ml(-1) was found to prevent enzyme inactivation by the products, although it increased the process time. Thus 60 U ml(-1) of enzyme completely converted the p-chlorophenol (into products) in 4 min in the absence of PEG. On the other hand, only 0.05 U ml(-1) of enzyme was required for this purpose in the presence of PEG but the process required 60 min. Peroxidase converts phenol molecules into free radicals. These free radicals then polymerize and get precipitated. As a further means of minimizing exposure of the enzyme to free radicals and enhancing the reusability, it was decided to remove the enzyme from reaction medium after 10 min. With this strategy, the bioaffinity layered peroxidase preparation could be reused five times without any loss of activity.     

Role of alpha-tocopherol and beta-carotene in ameliorating the fenvalerate-induced changes in oxidative stress, hemato-biochemical parameters, and semen quality of male rats

Role of alpha-tocopherol (vitamin E), beta-carotene and/or their combination as antioxidants against the toxicity of fenvalerate on blood hematology, free radicals, biochemical parameters, and semen quality were studied in male rats. Fenvalerate (20 mg/kg BW), vitamin E (100 mg/kg BW), beta-carotene (10 mg/kg BW), and vitamin E plus beta-carotene (100 + 10 mg/kg BW, respectively) were given alone or in combination with fenvalerate. The tested doses were given to rats every other day for 30 days. Results obtained showed that fenvalerate significantly (P < 0.05) induced free radicals in plasma and brain and insignificantly in liver and testes. While, vitamin E, beta-carotene alone and/or in combination decreased the levels of free radicals in plasma, liver, testes, and brain. The activities of glutathione S-transferase (liver), alkaline phosphatase (plasma and liver), aspartate aminotransferase (plasma, liver, and testes) and alanine aminotransferase (plasma and liver) were significantly (P < 0.05) increased due to fenvalerate administration. The activity of acetylcholinesterase was significantly (P < 0.05) decreased in brain and plasma, while plasma glucose, urea, creatinine, and bilirubin concentrations were significantly (P < 0.05) increased in rats treated with fenvalerate. Also, results showed a significant (P < 0.05) alterations in plasma proteins, hematological parameters, body weight, and relative weights of organs. Sperm concentration and motility (%) were significantly (P < 0.05) decreased, while dead and abnormal sperm increased in rats exposed to fenvalerate. Vitamin E, beta-carotene alone and/or in combination did not cause any changes in the investigated parameters, but improved semen quality and minimized the toxic effect of fenvalerate. The obtained results demonstrated the beneficial influences of vitamin E, beta-carotene alone and/or in combination in reducing the harmful effects of fenvalerate.     

Estimation of the cancer risk to humans resulting from the presence of cyclophosphamide and ifosfamide in surface water

Background, aim, and scope  

Anti-tumour agents and their metabolites are largely excreted into effluent, along with other pharmaceuticals. In the past, investigations have focused on the input and analysis of pharmaceuticals in surface and ground water. The two oxazaphosphorine compounds, cyclophosphamide and ifosfamide are important cytostatic drugs used in the chemotherapy of cancer and in the treatment of autoimmune diseases. Their mechanism of action, involving metabolic activation and unspecific alkylation of nucleophilic compounds, accounts for genotoxic and carcinogenic effects described in the literature and is reason for environmental concern. The anti-tumour agents cyclophosphamide (CP) and ifosfamide (IF) were not biodegraded in biodegradation tests. They were not eliminated in municipal sewage treatment plants. Degradation by photochemically formed HO radicals may be of some relevance only in shallow, clear, and nitrate-rich water bodies but could be further exploited for elimination of these compounds by advanced oxidation processes, i.e. in a treatment of hospital waste water. Therefore, CP and IF are assumed to persist in the aquatic environment and to enter drinking water via surface water. The risk to humans from input of CP and IF into surface water is not known.     

大气压降膜DBD等离子体去除废水中四环素

水体中抗生素类药物污染主要来源于人体和动物的大量使用,为改善水环境,降低和去除水中抗生素类药物,设计了可进行较大体积水中四环素的有效去除大气压降膜介质阻挡放电(dielectric barrier discharge)装置,研究了等离子体对四环素模拟液的降解特性,并分析了其降解机理。结果表明,当初始浓度为100 mg·L⁻¹,等离子体处理四环素溶液10 min,去除率为90%,化学需氧量去除率为45%,能量效率达到3.16 g·(kWh)⁻¹。较高的能量效率源自放电产生大量的活性物种(高能电子、离子、自由基等)。采用紫外可见分光光度法和液相色谱-质谱等检测方法对水样进行了分析,当等离子体放电处理2 min后,四环素溶液中开始生成新的物质,随着放电时间的延长,新物质种类和产量也随之逐渐增加,直至水中四环素接近完全降解。研究结果为实现大面积、工业级的有机抗生素废水的处理,保护水生生态环境提供了参考。     

Bioaccumulation and physiological effects of tetrabromobisphenol A in coontail Ceratophyllum demersum L

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants. In the present study, the accumulation of TBBPA and its consequent biological responses were examined in coontail (Ceratophyllum demersum L.) over 14 days' exposure. Most of the TBBPA was accumulated after 4d exposure and TBBPA concentration in plant increased with increasing TBBPA concentration in growth solution (R(2)=0.99). By using electron paramagnetic resonance (EPR), we found that the TBBPA exposure significantly increased total free radicals generation in the plants. A good positive relationship (R(2)=0.99) was found between the free radicals formation and accumulation level of TBBPA in plant. Lipid peroxidation was enhanced and chlorophyll content showed declined after TBBPA exposure. The activities of superoxide dismutase (SOD), peroxidase (POD), and the contents of glutathione were also detected. The results suggest that TBBPA accumulation in C. demersum induces oxidative stress and the level of tolerance depends on the antioxidative capacity of the plants.     

有机配体对铁电絮凝体系中羟基自由基氧化降解苯胺的影响

铁电絮凝(Fe-EC)是一种高效的水处理方法,但其中有机污染物的去除机制尚不明晰。为研究有机废水中常见的有机配体对铁电絮凝过程中羟基自由基(·OH)产生以及有机污染物降解的影响,采用了对照实验、淬灭实验和电子自旋共振（ESR）等测试方法。结果表明：草酸(H₂C₂O₄)和乙二胺四乙酸(EDTA)能有效促进铁电絮凝对苯胺(AN)的氧化降解,而·OH是起主要作用的活性氧化物;草酸和EDTA体系中主要存在的Fe(Ⅱ)络合物浓度与羟基自由基产率成正相关关系,1 mol的Fe(Ⅱ)-EDTA²⁻会产生235 mmol的·OH,是草酸的9倍;EDTA会与污染物竞争羟基自由基。进一步分析可知,在铁电絮凝体系中,EDTA的浓度为0.05 mmol·L⁻¹时,对苯胺氧化降解的促进效果最佳。以上研究结果可为认识铁电絮凝中污染物的去除机制提供参考。     

The study of lag phase and rate improvement of TCE decay in UV/surfactant systems

The photodegradation of trichloroethene (TCE) in surfactant micelles was investigated. The decay of TCE was studied in the Rayonet RPR-200 merry-go-round photoreactor, at 253.7 nm monochromatic ultraviolet (UV) lamps, in the presence of surfactants. Surfactants are used as additional hydrogen sources to improve the photodegradation rates of TCE. About three times the rate increment is observed in the presence of Brij 35 surfactant micelles than in water alone. The increasing concentrations of H+ and Cl- indicate that they are the final products of TCE photodegradation (i.e. photodechlorination is the dominant mechanism in this system). A lag phase is observed at the beginning of the degradation, but the duration of the lag phase is apparently reduced as the initial pH increases. Because the overall decay of TCE is also found faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. The photodecomposition of TCE in surfactant micelles is also proven to be a clean and effective process. It generates no chlorinated by-products or intermediates during the process, and TCE is fully decomposed within a reasonable time.     

Gas-phase mechanism for dioxin formation

We consider the formation of dioxin in the gas phase through the combination of phenoxy radicals in the context of a recently published scenario regarding the possibility of forming highly chlorinated benzenes in poorly mixed systems. It is demonstrated that the production of free chlorine in fuel lean combustion systems and subsequent mixing and quenching with fuel rich mixtures leads to chlorine atoms as the main reactive radicals. Under such conditions high concentrations of chlorinated phenoxy radicals can be formed. This leads to the formation of concentrations of dioxins that are consistent with recent measurements of Sidhu et al. [Combust. Flame 100 (1995) 11]. It suggests that there may be a gas-phase channel for the dioxin formation in addition to the usually assumed surface catalyzed process.     

DBD结构对船用LNG发动机尾气CH4氧化脱除的影响

为提高等离子体氧化CH₄的脱除效率,同时避免放电过程中副产物NO_x的生成,在模拟天然气 (LNG) 发动机排气中,研究了介质阻挡放电 (DBD) 反应器电极结构参数对CH₄脱除效率、CO₂选择性及NO_x生成的影响及其机理。结果表明：增大电极直径使得气隙中折合场强E/N提高,增加了·O和·OH自由基的生成,促进了CH₄的氧化,提高了CO₂选择性;内电极直径的增大使E/N在气隙中分布更加集中,抑制了N₂(X, v)和N自由基的生成,减少了副反应的发生。与圆杆电极相比,螺纹电极的螺牙顶部附近具有过高的电场强度,从而促进N自由基的生成并抑制·O自由基的产生,故圆杆电极比螺纹电极具有更高的CH₄脱除效率及更低的NO_x生成。电极长度过长降低了折合场强以及电子平均能量,不利于氧化性活性粒子生成,导致CH₄脱除效率和CO₂选择性降低,同时增加了N₂(X,v) ,也使得NO_x增加。本研究可为提高低温等离子体协同催化剂促进甲烷还原NO_x系统的脱除效率,降低DBD反应器能耗提高能源利用率提供参考。     

Characteristics and sources of environmentally persistent free radicals in PM2.5 in Dalian,Northeast China: correlation with polycyclic aromatic hydrocarbons

Environmental Science and Pollution Research - Environmentally persistent free radicals (EPFRs) are an emerging class of environmental hazardous contaminants that extensively, stably exist in...     

可见光/石墨相氮化碳/溴化氧铋/过二硫酸盐体系高效降解活性蓝19的增强效应及路径

为探究光催化降解蒽醌染料活性蓝19(RB19)过程中蒽醌的光敏特性对去除率的影响,以石墨相氮化碳/溴化氧铋(g-C₃N₄/BiOBr)为光催化材料,引入光照(vis)与过二硫酸盐(PS),构成协同催化氧化体系,考察光激发产物半醌自由基(Q⁻·)的形成及其参与、增强体系氧化能力的作用机制,采用单因素(材料投加量、初始pH、活性蓝19初始质量浓度、过硫酸盐投加量、光照强度)分析方法,探究Q⁻·增强效应的影响,使用降解动力学方法及LC/MS评估降解后废水的毒性。结果表明：Q⁻·的形成不仅加速了过硫酸盐的活化过程,Q⁻·与氢醌(H₂Q)、醌(Q)形成的循环作用也强化了材料的光催化效应,在模拟太阳光照射下(300 W),催化剂用量为0.1 g·L⁻¹和PS投加量为400 mg·L⁻¹时,Q⁻·引发的长链式自由基反应使该体系在 80 min内对40 mg·L⁻¹的RB19的降解率可达到100%;反应条件对催化效果影响的大小顺序为材料投加量>初始pH>RB19初始质量浓度>过硫酸盐投加量>光照强度;Q⁻·中间体的形成有效提高了体系内自由基的含量,是反应后废水毒性显著降低的主要原因。由此可知,体系内Q⁻·所引发的自降解自循环、长链式自由基效应是实现RB19高效降解的主要因素。本研究结果可为开发蒽醌类染料废水处理技术的开发及实际应用提供参考。