Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere and troposphere

The hydroxyl radical (?OH) has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health. Nevertheless, high reactivity, low atmospheric abundance, determination of hydroxyl, and hydroperoxyl radical's quantity is very difficult. In the atmosphere and troposphere, hydroperoxyl radicals (HO₂) are closely demanded in the chemical oxidation of the troposphere. But advances in technology have allowed researchers to improve the determination methods on the research of free radicals through some spectroscopic techniques. So far, several methods such as laser-induced fluorescence (LIF), high-performance liquid chromatography (HPLC), and chemical ionization mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals. In this systematic review, we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals. The primary goal of this review is to deepen our understanding of the functions of the most critical free radical (?OH, HO₂) and also understand the currently used methods to quantify them in the atmosphere and troposphere.     

光照下铜离子对水中氢氧自由基生成量的影响

研究了水溶液中铜离子与抗坏血酸、柠檬酸盐及藻等配合体系在高压汞灯光照下产生氢氧自由基的情况,其中铜与抗坏血酸系统反应最强,高压汞灯光照增强了铜与抗坏血酸反应产生氢氧自由基的过程,高压汞灯光照时所产生的自由基量为不光照时的6～7倍。同时铜(或抗坏血酸)单一的水溶液在光照条件下也能产生氢氧自由基。铜离子与柠檬酸钠溶液混合在光照下能产生氢氧自由基;铜离子与藻液混合能加倍藻液中氢氧自由基的产生。     

水体中常见无机阴离子对TiO_2薄膜光催化还原Cr(Ⅵ)的影响

选择了5种水体中常见的阴离子(Cl~-,SO_4~(2-),HCO_3~-,NO_3~-以及HPO_4~(2-)/H_2P_4~-),分别考察了其对TiO_2薄膜光催化还原模拟Cr(Ⅵ)废水的影响.从上述离子的光吸收,对·OH的捕获作用以及与Cr(Ⅵ)的竞争吸附三个方面讨论了上述离子影响TiO_2薄膜光催化还原Cr(Ⅵ)速率的原因.结果表明,体系酸性越强,越有利于Cr(Ⅵ)的还原;在pH值约为6时,HCO_3~-,Cl~-和SO_4~(2-)对TiO_2薄膜光催化还原Cr(Ⅵ)具有促进作用,NO_3~-具有抑制作用,H_2PO_4~-/HPO_4~(2-)在低浓度时具有促进作用,而在高浓度时具有抑制作用.造成上述结果的主要原因是Cl~-,SO_4~(2-)和HCO_3~-具有较强的·OH捕获作用和在TiO_2表面较低的吸附能力;H_2PO_4~-/HPO_4~(2-)在TiO_2表面具有较强的吸附能力;NO_3~-对紫外光吸收作用降低了TiO_2表面的紫外光强度以及自身光化学反应产生了·OH.     

DBD降解CF2ClBr过程中自由基与电子能量

利用介质阻挡放电方法对环境污染物ＣＦ₂ＣｌＢｒ进行了等离子体降解的研究．在前人对该体系的降解产物分析及活性粒子推测的基础上,采用动态反应装置得到了等离子体的发射光谱,进一步确证了等离子体系中出现的ＣＦ₂、ＣＦＣｌ、Ｆ、Ｃｌ、Ｂｒ等主要自由基,并从中推出了等离子态气体可能发生的自由基反应．同时通过发射光谱的分析,近似得到该体系的平均电子能量约为２．４２ｅＶ     

Modelling of stem biomass accumulation in Pinus densiflora seedlings exposed to aqueous-phase OH radicals generating mist

The present study aimed to evaluate the short-term biomass accumulation of forest trees exposed to wet acidic depositions. A hierarchical Bayesian model of tree growth was developed based on the data of a short-term experiment in which 2-year-old Japanese red pine (Pinus densiflora Sieb. et Zucc.) seedlings were exposed to aqueous phase OH radicals generated by an iron-oxalate-H₂O₂ mist (a pseudo-polluted dew) over two growing periods. We conducted a statistical comparison of tree growth between the control and pollution treatment groups by using the growth model incorporated the random effects due to the unknown characteristics of each seedling. The variability among seedlings is expressed in this model by the posterior probabilistic distributions of unobserved dry weight of a stem cohort before exposure treatment. The analysis of the effects of pollution treatment on the stem growth revealed that this treatment decreases the biomass allocation in the current year stems. However, the effects on the relative growth rate of pre-existing stems were unclear. Based on these results, we can speculate that in a polluted environment, the short-term growth of the young stems in the seedlings inhibited by pollution treatment, thereby resulting in the slowdown of long-term biomass accumulation. This can explain the patterns observed in the declining Japanese red pine forests that are subjected to radical dot" title="radical dot" border="0">OH-generating dews in the polluted area of western Japan.     

烟气条件对直流电晕自由基簇射NO氧化过程的影响

运用以湿空气为自由基源物质的直流电晕自由基簇射系统,研究了烟气在反应器内的滞留时间、烟气流速和NO浓度对NO氧化过程的影响.结果表明:烟气流速的增加会抑制电晕放电的发展,而烟气中NO浓度的增加则使放电变得更加容易.NO的氧化受烟气在反应器内滞留时间的影响较小,而它受烟气流速的影响较大.在2W的输入功率下,当烟气在反应器内的滞留时间从8.5s增加到34.2s时,NO的氧化率只从54.5 %提高到57.6 %.而在1.7W·h/m³的能量密度下,当烟气流速从1.4cm/s增加到6.3cm/s时,NO的氧化率从60.0%减少到38.6%,能量利用率也从20.8g/(kW·h)下降到了13.3g/(kW·h).在湿空气流量一定的情况下,NO初始浓度存在一个最佳值,本实验中最佳的NO浓度为100×10^-6左右.     

天然水体腐殖质对双酚A光降解影响的研究

以中压汞灯模拟太阳光光源,研究了双酚A(BPA)在水体腐殖质中的光降解过程,探讨了不同来源的腐殖质、腐殖质浓度、BPA初始浓度、溶解氧等因素对BPA光解速率的影响,实验结果表明,BPA在纯水体系中直接光解很慢,但在腐殖质溶液中光解迅速,符合拟一级动力学反应,改变BPA初始浓度对BPA光解速率的影响不明显,增大溶解氧浓度会抑制BPA光解,通过活性氧分子探针鉴定了腐殖质吸收光辐射产生的羟基与单线态氧,利用GC-MS鉴定了双酚A在Nordic湖富里酸(NOFA)中的光敏化降解产物,推测出BPA敏化降解的可能历程为能量转移导致的直接光解、羟基加成和羟基氧化。     

甲醛致DNA断裂作用的机制及修复的研究

应用单细胞凝胶电泳技术研究了甲醛致DNA断裂作用、作用机制以及断裂的修复.结果表明,甲醛在低浓度下可以诱导DNA的断裂(P<0.01);该断裂作用可以显著地被羟基自由基(·OH)清除剂甘露醇和二甲基亚砜抑制(P<0.01),以及受到超氧阴离子自由基(O·-2)清除剂超氧化物歧化酶(SOD)显著抑制(P<0.01),但其抑制效果要弱于甘露醇和二甲基亚砜.甲醛引起DNA断裂作用是通过活性氧自由基介导的,且在90min时基本上可被完全修复.     

催化臭氧化饮用水中甲草胺的研究

利用Fe2+、Mn2+和腐殖酸对水中甲草胺进行了催化臭氧化研究.实验表明,少量的催化剂就可促进甲草胺的降解,过量则会产生抑制作用.深入研究表明,甲草胺的降解与具有极强氧化能力的羟基自由基有关.     

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.