大气中挥发性含氧有机物研究进展

大气中的挥发性含氧有机物(oxygenated volatile organic compounds,OVOCs)主要由醛、酮、醇、酸、醚、酯及极其活泼的烯醛、烯酮等化合物组成.挥发性含氧有机物对大气化学的研究起着十分重要的作用:一方面OVOCs拥有较高的反应活性可直接参与大气光化学反应过程,进而形成臭氧等强氧化性的污染物.另一方面OVOCs对二次有机气溶胶的形成(secondary organic aerosol,SOA)影响显著,是SOA生成的重要前体物.研究表明,OVOCs不仅在大气光化学反应中起到重要作用,而且会对人体造成一定危害,具有致癌、致畸、致突变等危害,因此受到国内外学者的广泛关注.OVOCs的来源广泛,其中主要包括自然源、人为源以及大气光化学反应的二次转化过程.其在大气中的浓度变化范围大,反应活性高,且许多挥发性含氧有机物寿命短、含量低.这些特点使得对其采样及测量方法有着非常严格的要求:检测方法应有较高的灵敏度,且能实现痕量水平的分析;采样及分析过程需避免目标物的降解或转化.挥发性含氧有机物的分析方法包括离线分析法与在线连续分析法,其中离线分析法包括化学衍生法、气相色谱法(GC)、高效液相色谱法(HPLC)等方法,在线连续分析法包括在线气相色谱技术、质子转移质谱(PTR-MS)等方法,其中2,4-二硝基苯肼(DNPH)-高效液相色谱(HPLC)法应用最广.     

乙二醛与氨液相化学反应的若干影响因素

大气中乙二醛是二次有机气溶胶的形成推进剂,氨是雾霾生成的促进剂.本论文采用高效液相色谱-质谱联用仪器、紫外可见分光光度计和傅立叶红外光谱仪探究乙二醛与氨的液相化学反应,研究乙二醛浓度、氨水的浓度和溶液pH值等环境因素对反应产物的影响.结果发现,乙二醛与氨液相反应主要生成的是2,2'-联咪唑,利用紫外可见分光光度计在287 nm附近测得有较强的吸收峰.乙二醛与氨混合能快速反应生成2,2'-联咪唑,反应后溶液的吸光度随着乙二醛浓度增大呈现先增大后缓慢减小的趋势.随氨水浓度的增大,反应产物溶液吸光度先增大后不变.此外,强酸性的条件不利于2,2'-联咪唑的生成.     

氧化及未氧化脂肪对热反应水溶性产物的影响

研究脂肪氧化对热反应肉香味形成产生影响的机理,通过褐变颜色、元素分析、热降解挥发性成分分析,确定氧化及未氧化脂肪对“半胱氨酸-葡萄糖”模型反应体系形成的水溶性产物的影响.结果表明,该模型反应的水溶性产物以小分子物质(小于3 000 Da)为主,但构成水溶性产物的大分子物质(大于3 000 Da)和小分子物质均对其颜色有贡献.“半胱氨酸-葡萄糖”反应体系中加入鸡脂或氧化鸡脂后,因脂肪降解产生的小分子羰基化合物参与美拉德反应,造成热反应程度增强,表现为水溶性反应产物的颜色加深、C/N和C/S升高,热降解产生的含硫化合物、含氮杂环及含氧杂环化合物的含量升高,二次加热产香能力增强.与未氧化鸡脂相比,添加氧化鸡脂时,上述变化更为显著.     

1,3-二羰基化合物的区域和化学选择性氟化

以廉价易得的1-氯甲基-4-氟-1,4-重氮化二环[2.2.2]辛烷双(四氟硼酸)盐为氟源,以1,3-二羰基化合物为反应原料在乙醇和水的混合溶剂中可以高效地发生α-位点的区域选择性氟代反应;通过对氟源的用量和反应时间的调控,可以高化学选择性地构建一系列2-单氟代和2,2-双氟代的1,3-二羰基目标化合物.该反应无需过渡金属催化剂、碱性添加剂以及额外的氧化,在室温条件下即可通过单电子氧化还原历程完成,且可进行克规模级别的放大量生产,提供了一种方便而实用的自由基氟化新方法.     

太原市采暖大气挥发性有机物(VOCs)污染特征

本研究于2017年10月和12月使用苏玛罐对太原市采暖期前及进入采暖期后大气VOCs进行采集,并用气相色谱-质谱仪/火焰离子检测器(GC-MS/FID)对57种VOCs进行分析。结果表明,进入采暖期后,VOCs的总体浓度由51. 98μg/m~3升高至102. 43μg/m~3,在两个阶段中,各类VOCs均呈现烷烃芳香烃烯烃炔烃的趋势,苯和丙烯最为显著;比值分析结果得出,太原市受本地排放影响较大,且燃烧源为主要排放源。利用气溶胶生成系数(FAC)估算两个阶段的SOA的生成潜势,发现进入采暖期后,SOA生成潜势有大幅度的升高,芳香烃对SOA的贡献最大,且甲苯、苯和间/对-二甲苯是对SOA生成贡献大的物种。     

图书推介

<正>大气二次有机气溶胶污染特征及模拟研究郝吉明,吕子峰,楚碧武等著。科学出版社,2015年2月第1版,定价:98.00元。二次有机气溶胶是大气颗粒物的主要成分之一,对人体健康、空气质量、气候变化等都有严重影响。本书系统地阐述了二次有机气溶胶的概念、形成机制、影响因素、研究方法及模型模拟等。基于外场观测的颗粒物、挥发性有机物等数据,本书研究了典型地区北京的二次有机气溶胶大气污染特征,指认了对二次有机气溶胶生成贡献大的挥发性有机     

上海地区 2017 年夏季大气中羰基化合物的空间分布特征

使用实验室自主研发的多通道含氧挥发性有机物 (oxygenated volatile organic compound, OVOC) 远程控制采样器, 于 2017 年 8 月 4---7 日 对上海地区 20 个监测站点在早高峰 (6:00---9:00) 时段同步采集大气中 20 种羰基化合物, 并利用 2, 4-二硝基苯肼 (dinitrophenyl- hydrazone, NDPH)/高效液相色谱 (high performance liquid chromatography, HPLC) 法进行分析. 研究结果表明: 上海及其周边地区夏季大气中总羰基化合物浓度水平为 14.34$\sim$ 106.15 $\mu $g/m$^{3}$, 并呈现西部高、东南低的空间分布特征; 各地区浓度水平有明显差异, 其中浦东临港、崇明各采样点浓度较低, 金山枫泾、苏州工业园区最高. 甲醛、 乙醛和丙酮是大气中最主要的羰基化合物, 三者共占羰基化合物总量的 68%. 甲醛、乙醛、丙醛之间具有较好的相关性, 苯甲醛、庚醛、 辛醛、壬醛、癸醛之间也存在一定的正相关性, 说明它们之间有着相似的来源. 羰基化合物臭氧生成潜势 (ozone formation potential, OFP) 为 68.01$\sim $326.83 g/m$^{3}$, 其中甲醛贡献最大, 乙醛次之, 二者占羰基化合物臭氧生成潜势总量的 92.93%.     

羰基化合物化学性质教学思考

羰基化合物的官能团为C=O,包含有醛酮、羧酸及其衍生物、β-二羰基化合物,羰基化合物可发生亲核加成反应、亲核取代、α-H反应、氧化和还原反应等;我们在教学中采用了探究式教学,使学生从结构去更好理解和掌握羰基化合物的化学性质,从而达到掌握和熟练应用羰基化合物化学性质的目的.     

低共熔物中的快速卤素交换反应

在绿色化学的研究中,低共熔物越来越受到重视.利用低共熔物作为反应介质和氯离子源,以α,α-二溴代羰基化合物为原料,通过室温下的卤素交换反应,在较短的时间内,可以制备α,α-二氯代羰基化合物,二氯代产物产率为76%~85%.在低共熔物中进行的卤素交换反应,原料相对易得,反应温和,具有快速、简便等优点,比较接近绿色化学的要求.     

过渡金属催化醇的氧化在氮杂环化合物合成中的应用进展

醇氧化后生成的羰基化合物可以与胺形成亚胺中间体,再发生后续的环化反应,因此醇的氧化反应已被广泛地用于氮杂环化合物的合成.根据长期以来的研究经验,从不同类型氮杂环化合物产物出发,对过渡金属催化醇的氧化反应在合成氮杂环化合物中的应用进行了分类和综述,其中着重介绍了过渡金属催化醇的需氧和脱氢氧化在合成氮杂环化合物中的应用进展.     

An amorphous solid state of biogenic secondary organic aerosol particles

Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90?billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.     

大气二次有机气溶胶研究进展

 大气二次有机气溶胶（SOA）严重影响着空气质量、大气辐射平衡和人体健康等,对SOA生成和控制的研究对于揭示颗粒物污染成因、为打赢蓝天保卫战提供决策依据都具有重要意义。但由于SOA的组成成分和生成过程复杂、来源繁多、具体机理难以识别,有关SOA的研究仍然面临着众多挑战。在调研近2年表在环境及大气化学等领域的国际重要学术期刊上的研究成果的基础上,总结了在SOA的分子组成、污染特征、前体物或来源、生成与老化过程的机理、关键影响因素、对大气光学性质和人体健康的影响等方面的研究进展。     

Atmospheric oxidation capacity sustained by a tropical forest

Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere, which are removed by oxidation reactions and deposition of reaction products. The oxidation is mainly initiated by hydroxyl radicals (OH), primarily formed through the photodissociation of ozone. Previously it was thought that, in unpolluted air, biogenic VOCs deplete OH and reduce the atmospheric oxidation capacity. Conversely, in polluted air VOC oxidation leads to noxious oxidant build-up by the catalytic action of nitrogen oxides (NO(x) = NO + NO2). Here we report aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest. Our data reveal unexpectedly high OH concentrations. We propose that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NO(x) air through reactions of organic peroxy radicals. Computations with an atmospheric chemistry model and the results of laboratory experiments suggest that an OH recycling efficiency of 40-80 per cent in isoprene oxidation may be able to explain the high OH levels we observed in the field. Although further laboratory studies are necessary to explore the chemical mechanism responsible for OH recycling in more detail, our results demonstrate that the biosphere maintains a remarkable balance with the atmospheric environment.     

VOCs催化反应过程与反应机理研究现状

论述了挥发性有机污染物(VOCs)催化反应过程机理研究的现状,包括催化剂的表征、催化过程研究方法以及不同的研究体系。催化剂表征使用原位技术以及X射线吸收精细结构(XAFS)方法可以更好地阐述催化剂在催化过程中的作用与机制。催化过程研究主要包括催化反应动力学模拟(Power-rate Law、Mars-van Krevelen Model、Langmuir-Hinshelwood),反应产物监测(原位红外技术、原位核磁技术、暂态技术、同位素示踪技术),量子化学计算等。其中,反应动力学是使用较为广泛的研究催化反应机制的技术之一。反应产物监测可以得到直观的认识,获得了广大学者的关注。量子化学计算只作为论证。     

Second organic aerosol formation by irradiation of α-pinene-NO<Subscript>x</Subscript>-H<Subscript>2</Subscript>O in an indoor smog chamber for atmospheric chemistry and physics

Ozone（O3） and secondary organic aerosol （SOA） are considered to be the most serious secondary air pollutants of concern in most metropolitan areas, as well as for Beijing. In this study, 03 and SOA formation potential of α-pinene, the most abundant biogenic VOCs, is investigated at Tsinghua Indoor Chamber Facility. The experiments were conducted under atmospheric relevant HCs/NOx ratios in both presence and absence of ammonia sulfate seed aerosol. A Scanning Mobility Particle Sizer system （3936, TSI） and a Condensation Particle Counter （3010, TSI） were used to study the SOA formation and a gas chromatograph （GC） equipped with a DB-5 column and a flame ionization detector （FID） was used to measure α-pinene simultaneously. The results show that the presence of ammonia sulfate seed aerosol did not change the formation trend of 03, but significantly contribute to SOA formation. A strong linear relationship （r^2 = 0.90） between SOA yield enhancement （△Y＊） and surface concentration of seed aerosol （PM1, s）has been found, denoting that the PMi, s is the control factor for SOA yield enhancement. And the possible reason for the enhancement is acid-catalyzed heterogeneous reactions.     

Halocarbons produced by natural oxidation processes during degradation of organic matter

Volatile halogenated organic compounds (VHOC) play an important role in atmospheric chemical processes-contributing, for example, to stratospheric ozone depletion. For anthropogenic VHOC whose sources are well known, the global atmospheric input can be estimated from industrial production data. Halogenated compounds of natural origin can also contribute significantly to the levels of VHOC in the atmosphere. The oceans have been implicated as one of the main natural sources, where organisms such as macroalgae and microalgae can release large quantities of VHOC to the atmosphere. Some terrestrial sources have also been identified, such as wood-rotting fungi, biomass burning and volcanic emissions. Here we report the identification of a different terrestrial source of naturally occurring VHOC. We find that, in soils and sediments, halide ions can be alkylated during the oxidation of organic matter by an electron acceptor such as Fe(III): sunlight or microbial mediation are not required for these reactions. When the available halide ion is chloride, the reaction products are CH3Cl, C2H5Cl, C3H7Cl and C4H9Cl. (The corresponding alkyl bromides or alkyl iodides are produced when bromide or iodide are present.) Such abiotic processes could make a significant contribution to the budget of the important atmospheric compounds CH3Cl, CH3Br and CH3I.     

环境持久性自由基的研究进展

环境持久性自由基(environmental persistent free radicals, EPFRs)是一类新型的环境风险物质, 能在大气环境中持久存在, 并具有顺磁稳定性. 主要概述了EPFRs的特征、形成机理以及影响EPFRs 形成的各种因素, 总结了EPFRs 的环境持久性和毒性对人体健康的危害, 并介绍了EPFRs 的潜在环境应用, 以及利用EPFRs 激活某些化合物产生活性氧对有机污染物进行降解等.     

大气复合污染新型观测技术研究进展

 大气中的污染物种类繁多,来源和演化过程复杂,而且污染物之间在一定的条件下发生相互作用,形成一种彼此耦合的复杂污染体系,被称为复合污染。为了研究大气复合污染的形成原因及其控制手段,必然要求对各种大气污染的主要物种浓度进行测量,特别是超细粒子、有机气溶胶和挥发性有机物组分复杂,对检测技术要求较高。介绍了针对大气复合污染的新型观测技术,综述了以下3项技术的发展：超细气溶胶颗粒物观测新技术、气溶胶有机物组分分析新技术和挥发性有机物分析新技术,同时综述了大气复合污染的其他监测手段。     

A kinetic study of the reaction of ozone with ethylene in a smog chamber under atmospheric conditions

Ozone is one of the key species in the processes of atmospheric chemistry, which can be taken as an indicator of oxidation capacity in the troposphere. The reaction of ozone with reactive gases is an important process in the troposphere. Experimental simulation equipment of smog chamber for atmospheric reactions is used to study the reaction of ozone with ethylene in real atmospheric environment with ozone concentrations of 100―200 ppb. The concentrations of ozone and ethylene were moni-tored during the reaction with the combination of Model 49C-O_3 Analyzer and GC-FID. A rate constant of 1.01×10~(-18) (cm~3·mol~(-1)·s-(~1)) was obtained at 286.5 K, under condition of which the half-life of ozone was 88 min. The results obtained from our experiments are in excellent agreement with those reported previously by other researchers under extremely low pressure in terms of matrixisolation technology. This demonstrates that our equipment of smog chamber for atmospheric reactions is reliable, which can be used for further research of the processes of atmospheric reactions.     

造纸污泥焚烧中Zn/Cu/Ni/Mn的热力学平衡分布

采用化学热力学平衡分析方法,应用造纸污泥实测数据预测了其焚烧中重金属(Ni、Mn、Zn和Cu)的迁移和转化规律.研究结果表明,考虑矿物质存且在低温条件下,造纸污泥焚烧中重金属Ni和Zn易与Fe2O3结合形成稳定的固体化合物,从而抑制了Ni和Zn的挥发性,而对Mn和Cu没有影响.焚烧温度为400—1800K范围内有矿物质存在条件下,Mn未出现其气体产物,而其他三种金属在高温条件下则以其气态单质或气态氧化物挥发进入大气环境.焚烧过程中只有小部分气态CuCl生成,未见其它气态金属氯化物;在焚烧温度为400—1800K条件下未发现金属硫化物或者硫酸盐生成,表明在有矿物质存在条件下S对金属的挥发性影响很小.在未考虑矿物质存在条件下,S在低温条件下易与重金属结合形成金属硫酸盐固体从而拟制了金属的挥发;随着温度的升高,Cl和重金属易形成金属氯化物气体,促进了金属的挥发特性,并且Cl对Cu的挥发影响较大,其次为Zn和Mn,影响较小的金属是Ni.从而根据污泥在不同焚烧温度下不同的产物形态进行重金属的污染控制.