Dissolution of beryllium in artificial lung alveolar macrophage phagolysosomal fluid

Dissolution of a lung burden of poorly soluble beryllium particles is hypothesized to be necessary for development of chronic beryllium lung disease (CBD) in humans. As such, particle dissolution rate must be sufficient to activate the lung immune response and dissolution lifetime sufficient to maintain chronic inflammation for months to years to support development of disease. The purpose of this research was to investigate the hypothesis that poorly soluble beryllium compounds release ions via dissolution in lung fluid. Dissolution kinetics of 17 poorly soluble particulate beryllium materials that span extraction through ceramics machining (ores, hydroxide, metal, copper-beryllium [CuBe] fume, oxides) and three CuBe alloy reference materials (chips, solid block) were measured over 31 d using artificial lung alveolar macrophage phagolysosomal fluid (pH 4.5). Differences in beryllium-containing particle physicochemical properties translated into differences in dissolution rates and lifetimes in artificial phagolysosomal fluid. Among all materials, dissolution rate constant values ranged from 10⁻⁵ to 10⁻¹⁰ g cm⁻² d⁻¹ and half-times ranged from tens to thousands of days. The presence of magnesium trisilicate in some beryllium oxide materials may have slowed dissolution rates. Materials associated with elevated prevalence of CBD had faster beryllium dissolution rates [10⁻⁷-10⁻⁸ g cm⁻² d⁻¹] than materials not associated with elevated prevalence (p < 0.05).     

催化湿式过氧化（CWPO）偶氮染料反应机理及降解历程研究

采用浸渍法制备出具有较高催化活性的催化剂CuO/γ-Al2O3,通过XRD、电镜等手段对催化剂进行了表征。降解了几种不同结构的偶氮染料,并通过改变CWPO的反应条件推断了其催化反应机理。采用紫外/可见分光光度计（UV-Vis）和傅里叶红外光谱仪（IR）等手段对染料降解过程进行跟踪和分析,对比染料处理前后紫外可见光谱与红...     

Modification of cloud condensation nucleus activity of organic aerosols by hydroxyl radical heterogeneous oxidation

The modification of cloud condensation nucleus (CCN) activity of saturated organic particles resulting from heterogeneous oxidation by OH radicals was studied. Submicron Bis-2-ethylhexyl sebacate (BES) and stearic acid particles were exposed to OH radicals in a reactor flow tube and CCN activity was monitored. The hygroscopicity parameter, κ, for monodisperse stearic acid and BES particles of 145–150 nm in size increased from <0.008 up to 0.08 as a result of OH exposures equivalent to atmospheric exposure timescales of several days to a week. The oxidation of stearic acid particles led to a 50% reduction in particle volume at high OH exposures, indicating an enhanced degree of volatilization of oxidation products compared to oxidized BES particles, along with possible shape/phase change. Surface tension measurements of water extracts of oxidized BES films showed a significant reduction in surface tension due to oxidation. Köhler calculations modeling the CCN measurements suggest that the surface active oxidation products play an important role.     

Automobile exhaust gas as a source of aqueous phase OH radical in the atmosphere and its effects on physiological status of pine trees

Free radical generation potential of automobile exhaust gas was examined by measuring hydroxyl (OH) radical photo-formation rates in exhaust gas-scrubbing water. Effects of automobile exhausts on physiological status of Japanese red pine trees (Pinus densiflora Sieb. et Zucc.) were also investigated to elucidate the mechanism how the free radicals derived from exhaust gas damage higher plants. Gasoline and diesel exhaust gases were scrubbed into pure water. Potential photo-formation rates of OH radical in aqueous phase (normalized to sun light intensity of clear sky midday on May 1 at 34°N) for gasoline and diesel cars were ave. 51 and 107 μM h⁻¹ m⁻³ of exhaust gas, respectively. Nitrite was a dominant source (ca. 70-90%) of photochemical formation of OH radical in both gasoline and diesel car exhausts. The scrubbed solution of diesel car exhaust gas was sprayed for six times per week to needles of pine tree seedlings in open top chambers. Control, exhaust + mannitol (added as OH radical scavenger), and nitrite + nitrate standard solution (equivalent levels existed in the exhaust gas) were also sprayed. Two months sprays indicated that the sprayed solutions of diesel exhaust and nitrite + nitrate caused a decrease of maximum photosynthetic rate and stomata conductance in pine needles while the control and exhaust + mannitol solution showed no effects on photosynthetic activities of pine needles. These results indicated that OH radicals generated mainly from photolysis of nitrite occurring in the scrubbing solution of exhaust gas are responsible for the decrease of photosynthetic activities of pine needles.     

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.     

深圳市秋季大气OH自由基总反应性测量及其构成分析

羟基自由基(·OH)总反应性(k_(OH))是大气中所有·OH反应物的浓度与其·OH反应速率常数乘积的总和,对k_(OH)的直接测量有助于识别未知的·OH反应物种及提升·OH收支分析的准确度.因此,本研究建立了一套基于激光光解-激光诱导荧光技术的k_(OH)在线测量系统(LP-LIF),利用紫外脉冲激光在流动管内光解臭氧产生·OH,采用激光诱导荧光技术实时测量其与采样进入流动管的活性气体反应而导致的·OH浓度衰减,通过对该衰减进行指数拟合得到采样气的k_(OH).经实验室测试,LP-LIF系统对k_(OH)的测量灵敏度为1.2 s~(-1),时间分辨率5 min.应用该系统对2018年秋季深圳地区的大气k_(OH)进行为期1个月的连续测量,结合同步观测的·OH反应物浓度数据发现,k_(OH)观测值在10～30 s~(-1)之间,主要来自一氧化碳(14%)、氮氧化物(26%)和一次排放的挥发性有机物(24%).此外,由未测量的·OH反应物贡献的k_(OH)平均约23%,且在夜间和早晚高峰时段贡献较高,推测其主要来自溶剂涂料、石化工业及LPG机动车排放.     

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.     

高级氧化技术在垃圾渗滤液处理中的应用

垃圾渗滤液是一种成分非常复杂的高浓度有机废水.本文介绍了高级氧化技术在垃圾渗滤液处理中的应用现状.主要包括Fenton氧化法、光化学催化氧化法、湿式氧化法、臭氧氧化法、超声氧化法、电化学氧化法、超临界水氧化法及等离子体技术在垃圾渗滤液处理中的应用,分析了高级氧化技术处理垃圾渗滤液的原理,探讨了它们的优缺点,并对高级氧化技术处理垃圾渗滤液应用的未来发展进行了展望.     

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。