Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

光助-电解锰渣/H2O2非均相体系氧化降解双酚S

以电解锰渣作为光催化剂构建非均相类光Fenton体系,采用双酚S为模型化合物,研究了该反应体系中双酚S氧化降解的降解机制及影响因素,并建立了·OH的生成速率模型以及溶解性有机质（DOM）影响的预测模型.结果表明,电解锰渣中具有催化效果的铁和锰的质量含量分别为1.49%和2.28%;相比UV、UV/电解锰渣、UV/H₂O₂和电解锰渣/H₂O₂体系,电解锰渣/UV/H₂O₂光Fenton体系对双酚S具有更好的氧化降解效果,双酚S的降解效果与电解锰渣投加量、H₂O₂浓度呈正相关,与pH值、双酚S初始浓度呈负相关;溶液中析出的Fe和Mn的浓度与pH值呈负相关,且电解锰渣/UV/H₂O₂氧化体系反应浸出的共存活性金属组分不利于双酚S降解;电子自旋共振和自由基淬灭实验发现电解锰渣/UV/H₂O₂体系中氧化降解双酚的主要活性物种是·OH.采用异丙醇构建了该体系中·OH的生成速率模型,计算可得·OH的生成速率R·^f_OH在3.22×10^-9~1.1×10^-8mol/（L·s）之间,与硝基苯拟合计算出的R·^f_OH（6.5×10^-9mol/（L·s））一致.双酚S降解效率随着DOM浓度的增加而降低.基于自由基稳态动力学理论建立了DOM存在下电解锰渣/UV/H₂O₂体系中双酚S降解的动力学预测模型,发现模型的预测值与实验值较好符合,说明DOM主要通过淬灭体系中的·OH影响双酚S的降解.     

氯氟烃替代物与OH自由基光化学反应

保护生物多样性生物多样性是人类社会赖以生存和发展的物质基础，保护生物多样性，保证生物资源的持续利用是一项全球性任务，也是全球环境保护行动计划的重要组成部分。按照生物多样性国际公约的定义，生物多样性“是指所有来源和形形色色的生物体，这些来源包括陆地、海...     

提高钙基吸着剂脱硫活性的试验研究

研究制备了两类吸着剂，一类在Ｃａ（ＯＨ）２中混入易潮解性盐和碱，另一类是Ｃａ（ＯＨ）２与燃煤飞灰的水合物。在积分式固定床反应器系统的脱硫活性测试表明，添加剂的吸湿作用加速了表面反应，添加剂与Ｃａ（ＯＨ）２的湿混干燥物活性较纯Ｃａ（ＯＨ）２可提高１～２５倍；飞灰和Ｃａ（ＯＨ）２的水合物可使活性提高达５倍，利用飞灰增强钙基脱硫剂的活性是可能且有效的途径。     

Measurement of total OH reactivity by laser-induced pump and probe technique—comprehensive observations in the urban atmosphere of Tokyo

Total OH reactivity was observed by use of the laser-induced pump and probe technique, and the urban air quality in Tokyo was diagnosed comprehensively. The concentrations of NO_x, CO, O₃, non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (OVOCs) were observed simultaneously. The observations were conducted in July and August 2003, and in January, February, May, and November 2004. Generally, the observed OH reactivity was higher than the calculated values derived using the observed concentrations of the trace species. The differences between the observed and calculated values in summer, spring, and autumn were approximately 30%. However, the difference in winter was smaller than those in the other seasons. In addition, while the differences observed in summer, spring, and autumn correlated with the total reactivity of the OVOCs (Σ_i k_OVOCi[OVOC_i](s⁻¹), k_i is rate constant of its compounds with OH), the correlations were not confirmed in the case of winter because atmospheric oxidation was less active and OVOCs levels were low in winter. These results suggest that the secondary products of the photochemical reactions in the atmosphere would be a missing sink for the OH loss process in the urban area.     

F-SnO2/GAC粒子电极的制备及其电催化性能

以颗粒活性炭（GAC）为载体,通过溶胶-凝胶法制备了经F^-掺杂改性的F-SnO₂/GAC粒子电极.采用扫描电子显微镜（SEM）、X射线能谱（EDS）、X射线衍射（XRD）、X射线光电子能谱（XPS）、循环伏安曲线（CV）对粒子电极进行了表征.并以罗丹明B（RhB）为目标污染物,考察该粒子电极的电催化性能.结果表明：F-SnO₂纳米颗粒均匀分布在GAC的内外表面,且结晶完整;经F^-掺杂改性后的SnO₂活性组分能够增加反应体系中的转变电荷量,提高电催化活性.当RhB质量浓度为300mg/L、初始pH 3、槽电压为9V、处理30min时,在500℃下煅烧2h的10% F-SnO₂/GAC粒子电极对RhB的脱色率和COD去除率达到了97.6%和89.0%.运用电子自旋共振技术（ESR）确定了电催化过程主要是以羟基自由基（·OH）的间接氧化来实现对污染物的去除.     

A hydroxyl radical detection system using gas expansion and fast gating laser-induced fluorescence techniques

An OH radical measurement instrument based on Fluorescence Assay by Gas Expansion(FAGE)has been developed in our laboratory.Ambient air is introduced into a low-pressure fluorescence cell through a pinhole aperture and irradiated by a dye laser at a high repetition rate of 8.5 k Hz.The OH radical is both excited and detected at 308 nm using A-X(0,0)band.To satisfy the high efficiency needs of fluorescence collection and detection,a 4-lens optical system and a self-designed gated photomultiplier(PMT)is used,and gating is actualized by switching the voltage applied on the PMT dynodes.A micro channel photomultiplier(MCP)is also prepared for fluorescence detection.Then the weak signal is accumulated by a photon counter in a specific timing.The OH radical excitation spectrum range in the wavelength of 307.82–308.2 nm is detected and the excited line for OH detection is determined to be Q_1(2)line.The calibration of the FAGE system is researched by using simultaneous photolysis of H_2O and O_2.The minimum detection limit of the instrument using gated PMT is determined to be 9.4×10~5molecules/cm~3,and the sensitivity is 9.5×10~(-7)cps/(OH·cm~(-3)),with a signal-to-noise ratio of 2 and an integration time of 60 sec,while OH detection limit and the detection sensitivity using MCP is calculated to be 1.6×10~5molecules/cm~3and 2.3×10~(-6)cps/(OH·cm~(-3)).The laboratory OH radical measurement is carried out and results show that the proposed system can be used for atmospheric OH radical measurement.     

纳米Fe3O4/H2O2降解诺氟沙星

采用纳米Fe3O4催化H2O2氧化降解水环境中的诺氟沙星.考察了溶液酸度、温度、催化剂和H2O2浓度对诺氟沙星降解的影响,对比不同底物在Fe3O4/H2O2体系中的降解情况,并进一步探讨了其反应机制.结果表明,溶液酸度显著影响诺氟沙星的降解率,在酸性条件下（pH=3.5）诺氟沙星的降解效率最高.诺氟沙星的降解率随纳米F...     

生物铁膜生物反应器（SMBR）处理生活污水的试验研究

试验研究了在SMBR中投加不同量氢氧化铁对出水水质以及膜污染的影响。结果表明,生物铁SMBR中随氢氧化铁投加量的增加,CODrr,NH3-N去除率略有提高;当氢氧化铁投加量为混合液中污泥浓度的0～5％时,TP去除率逐渐提高,在7％时急剧下降。试验条件下氢氧化铁最佳投加量为混合液污泥浓度的5％．此时半透膜压增长最慢,膜污染程度最轻。在3％～5％的投加量下生物铁具有良好的絮状结构,有效地降低了膜表面滤饼层阻力,并且缓解了膜孔堵塞的影响,然而当投加量增大到7％时,生物铁结构变得密实,削弱了生物铁对溶解性有机物和磷的吸附,加剧了膜污染．     

Electro-assisted regeneration of ion exchange resins

Electro-assisted regeneration (EAR) for the mixed bed of strongly acidic cation and weakly basic anion exchange resins with the Al(OH)3 suspension in a three-compartment cell was investigated. The desalination experiments were carried out to evaluate the characteristic of the regenerated mixed resins. Experimental results showed that the efficiency of resin regeneration was strictly dependent on the voltage, regeneration time, and feed regenerant flow rate. The amount of the effluent reached 50 times the volume of the resins bed, and the conductivity was less than 1.0 μs/cm. Compared to the conventional ER, the total effluent volume of EAR was about 1000 mL more than that of ER under the same conditions, and the outlet conductivity was significantly lower. The desalination and regeneration reaction mechanisms of the mixed resins indicated the regeneration efficiency of resin with Al(OH)₃ as the regenerant was much higher than that with H₂O.