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题名: 有机胺在颗粒物上的非均相反应及对颗粒物性质的影响
作者: 葛艳丽1
学位类别: 硕士
答辩日期: 2017-05
授予单位: 中国科学院大学
授予地点: 北京
导师: 刘永春
关键词: 有机胺,非均相摄取,非均相氧化,DTT 毒性 ; amines, heterogeneous uptake, heterogeneous oxidation, DTT toxicity
其他题名: Heterogeneous reaction of amines on particles and theeffects on their properties
学位专业: 环境工程
中文摘要: 大气中有机胺可参与新粒子生成、纳米和亚微米气溶胶的生长、棕色碳形成 和大气氮循环。颗粒态有机胺本身和降解产物还导致气溶胶对人体健康的不利影 响。然而,目前非均相反应过程对大气氮循环的贡献尚不清楚。尤其是,有机胺 在矿尘上的非均相反应以及颗粒相的有机胺的降解过程尚未报道,非均相反应及 降解产物的理化性质变化及毒性有待评估。因此,研究有机胺在颗粒物表面的非 均相反应过程具有重要意义。本论文以努森池质谱(KCMS)、原位衰减全反射傅 立叶变换红外光谱(in situ ATR-FTIR)和质子转移反应质谱(PTR-MS)为主要 研究手段,结合紫外可见分光光谱(UV-Vis)、透射电子显微镜(TEM)、扫描电 子显微镜(SEM)以及量化计算(Gaussian 09)等方法研究了有机胺在矿质颗粒 物上的非均相反应过程,初步探索了有机胺在颗粒物表面的氧化老化降解机制和 毒性变化。取得的主要成果如下: (1)获取了232-300 K 下甲胺(MA)、二甲胺(DMA)和三甲胺(TMA)在 高岭土表面反应的摄取动力学特征。300 K 下MA、DMA 和TMA 在高岭土上的 初始真实摄取系数分别为(2.27±0.26)10-3、(1.71±0.26)10-3 和(2.95±0.63)10-3, 反应性与其碱度强弱有关。L 酸性位是高岭土上有机胺的主要吸附位点。当温度 从300 K 降到232 K 时有机胺在高岭土上的摄取系数增加了3 倍。质量聚集主导 了有机胺在高岭土上的摄取。MA、DMA 和TMA 在高岭土上的吸附焓Hobs 分 别为-7.8 ± 0.8、-9.9 ± 2.9 和-9.4 ± 1.0 kJ·mol-1,对应的吸附熵Sobs 分别为-77.1±3.2、 -84.1±11.8 和-80.6±3.7 J·K-1·mol-1。矿尘上非均相摄取导致MA、DMA 和TMA 的大气寿命约为数小时至几天。该值略低于或与OH 氧化消耗有机胺的寿命相 当。 (2)在有机胺与铵盐的交换反应的基础上,进一步考察了颗粒相的有机胺在 干态条件下的非均相反应过程及其毒性变化。在颗粒态三甲胺的臭氧氧化反应中, 可生成HCHO、CH3N=CH2、HCOOH、CH3NO2、(CH3)2NCHO、CH3NHOH 和 CH3N(OH)CHO 等。据此提出了颗粒相有机胺的臭氧氧化降解机制。 (3)初步考察了颗粒态甲胺和二甲胺的硝化反应过程。原位红外光谱结合质 子转移反应质谱数据确认了甲胺和二甲胺硝化反应过程中产物亚硝胺的生成。 NO 的存在会改变有机胺硝化反应途径。NO2 与有机胺反应时,由于微量水导致 NO2-生成,进而与有机胺反应生成亚硝胺。而NO 共存时,NO 将会夺取NO2 与 胺形成的反应中间体[(CH3)2N---HONO]上的OH 最终形成亚硝胺。 (4)测定了臭氧氧化前后颗粒物的DTT 消耗速率,进而评估其产生活性氧物种的能力。空白校正后硝酸铵的DTT 消耗速率为(1.76 ± 0.166)×10-2 pmol·min- 1·μg-1,三甲胺硝酸盐的DTT 消耗速率为(1.47 ± 0.239)×10-2 pmol·min-1·μg-1,二 者的DTT 毒性无显著差异。三甲胺硝酸盐臭氧氧化后的DTT 消耗速率为(8.40 ± 1.250)×10-2 pmol·min-1·μg-1,相比前两者颗粒物的DTT 活性增加了约6 倍。由此 表明,颗粒态有机胺氧化后其毒性会在一定程度上增加。
英文摘要: Amines contribute to atmospheric reactive nitrogen (Nr) deposition, new particle formation, the growth of nano- and sub-micron particles and brown carbon formation. Particle-phase amines and the degradation products also are associated with the adverse health impacts of aerosols. However, the role of mineral dust in the chemical cycle of amines is unknown because the corresponding reaction kinetics are unavailable. In addition, the degradation mechinism of organic amines in particulate phase atmosphere is unclear, and the related toxicological evlution is required to be evaluated. Therefore, it is of great significance to study the heterogeneous reaction process of amines on the surface of particulate matter. In this thesis, the heterogeneous reaction process of organic amines on mineral dust, the aging mechanism of organic amines on the surface of particulate matter and the toxicological evolution were invesitigated using Knudsen cell mass spectrometry (KCMS), in situ attenuated total reflectance- infrared fourier transform spectroscopy (in situ ATR-FTIR), proton transfer reaction mass spectrometry (PTR-MS), ultraviolet-visible spectroscopy (UV-Vis), and quantum chemical calculation (Gaussian 09) and so on. The main results are: (1) The heterogeneous uptake of methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA) by kaolinite was investigated in the temperature range of 232- 300 K using a Knudsen cell reactor. Lewis acid sites on kaolinite were identified as dominant contributors to the uptake of amines. The initial effective uptake coefficients (eff) were (7.22±0.82)10-4, (7.59±1.13)10-4 and (2.65±0.56)10-3, respectively, for MA, DMA and TMA on kaolinite at 300 K, while they increased ~3-fold with decreasing temperature from 300 K to 232 K. The adsorption enthalpies (Hobs) of MA, DMA and TMA on kaolinite were -11.2±0.6, -17.2±3.7 and -12.1±1.3 kJ·mol-1, respectively, and the corresponding entropy values (Sobs) were -97.5±2.4, -117.6±14.0 and -90.4±4.7 J·K-1·mol-1. The lifetimes of MA, DMA and TMA attributable to heterogeneous uptake by mineral dust were estimated to be several hours to days. These values were slightly lower than or comparable to the lifetimes of amines consumed by OH oxidation. (2) The heterogeneous ozonidation of amines in particulate phase under dry condition and the subsequent changes in toxicity (DDT decay rate) of the products were investigated. After exchanged by TMA with (NH4)2SO4, NH4HSO4, NH4NO3 and NH4Cl, HCOOH, HCHO, CH3N=CH2, (CH3)2NCHO, CH3NO2, CH3N(OH)CHO, CH3NHOH and H2O were identified as products for O3 oxidation of particulate trimethylamine (TMA) on all the substrates based upon IR, quantum chemical calculation and PTR-MS results. A reaction mechanism was proposed to explain the observed products. (3) The nitration reaction process of methylamine and dimethylamine in particle phase was investigated. In situ infrared spectroscopy combined with proton transfer reaction mass spectroscopy confirmed the formation of nitrosamines in the nitrification process of methylamine and dimethylamine. The presence of NO changes the pathway of the nitrification. Specifically, when reacting with NO2, the presence of trace amounts of water causes NO2 -, subsequently leads to formation of nitroamines. However, in the presence of NO, NO reacts with the OH in the intermediate [(CH3)2N---HONO] formed by NO2 with the amine, and then results in nitrosamines formation. (4) Compared with ammonium and aminium salts, the oxidation potential of particulate aminium after ozone oxidation of particulate TMA increased significantly, with a DTT loss rate that increased from 1.76 ± 0.166 × 10-2, 1.47 ± 0.239 × 10-2 to 8.40 ± 1.250 × 10-2 pmol·min-1·μg-1. This work demonstrates that oxidation might be a degradation pathway of particulate amines in the atmosphere and the oxidation products in the particle phase are associated with modification of the adverse health impacts of aerosol particles.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/38622
Appears in Collections:大气污染控制中心_学位论文

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葛艳丽. 有机胺在颗粒物上的非均相反应及对颗粒物性质的影响[D]. 北京. 中国科学院大学. 2017.
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