对流层夜间化学研究

NO3自由基与N2O5是对流层夜间化学的关键物种。一方面NO3与O3等组分是夜间大气中的重要氧化剂,与它们的反应是生物排放挥发性有机物（VOCs）的主要汇;另一方面NO3与N2O5和雨滴或气溶胶颗粒物发生的异相反应则是大气中氮氧化合物NOx（NO,NO2）的主要清除过程,从而可以减轻对流层臭氧污染。研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和全面了解区域乃至全球大气自净能力有重要意义。本文总结了近年来有关夜间化学的研究成果,介绍了以NO3和N2O5为中心的基本夜间化学过程、对流层中NO3与N2O5的源与汇以及外场测量技术的最新研究进展,并提出了尚待解决的一些问题。     

对流层夜间化学研究

NO3自由基与N2O5是对流层夜间化学的关键物种。一方面NO3与O3等组分是夜间大气中的重要氧化剂,与它们的反应是生物排放挥发性有机物(VOCs)的主要汇;另一方面NO3与N2O5和雨滴或气溶胶颗粒物发生的异相反应则是大气中氮氧化合物NOx(NO,NO2)的主要清除过程,从而可以减轻对流层臭氧污染。研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和全面了解区域乃至全球大气自净能力有重要意义。本文总结了近年来有关夜间化学的研究成果,介绍了以NO3和N2O5为中心的基本夜间化学过程、对流层中NO3与N2O5的源与汇以及外场测量技术的最新研究进展,并提出了尚待解决的一些问题。     

对流层夜间化学研究

NO3自由基与N2O5是对流层夜间化学的关键物种.一方面NO3与O3等组分是夜间大气中的重要氧化剂,与它们的反应是生物排放挥发性有机物(VOCs)的主要汇;另一方面NO3与N2O5和雨滴或气溶胶颗粒物发生的异相反应则是大气中氮氧化合物NOx(NO,NO2)的主要清除过程,从而可以减轻对流层臭氧污染.研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和全面了解区域乃至全球大气自净能力有重要意义.本文总结了近年来有关夜间化学的研究成果,介绍了以NO3和N2O5为中心的基本夜间化学过程、对流层中NO3与N2O5的源与汇以及外场测量技术的最新研究进展,并提出了尚待解决的一些问题.     

活性卤素化学

活性卤素是大气中的重要物种,它能参与大气中的多种化学过程,对臭氧的损耗有重要影响,影响许多重要物种的源和汇,同时对大气硫循环和汞循环也产生影响,在大气化学中有着十分重要的作用.因此,对活性卤素化学的研究成为近年来国际大气化学研究的重要前沿.本文总结了近年来活性卤素化学实验和理论的研究进展,重点介绍了活性卤素在臭氧损耗中的作用及其大气循环反应过程;综述了重要活性卤素物种的产生和探测、活性卤素光化学反应和非均相反应实验研究;总结了近年来关于活性卤素化学的理论研究,包括活性卤素与水、硫、HO、HO2、烷基氧和烷基过氧自由基、氮氧化物、汞及其它物种的耦合研究.最后,对活性卤素化学的实验和理论研究进行了展望,提出了尚待深入开展研究的一些重要科学问题.     

对流层大气过氧自由基实地测量的技术进展及其在化学机理研究中的应用

大气过氧自由基化学是对流层大气化学的重要组成部分,对于理解大气氧化性、光化学臭氧和二次有机气溶胶生成等核心科学问题具有重要意义。基于实地测量,准确掌握大气过氧自由基的浓度水平、进行相关化学行为分析以及实测结果模拟分析一直是大气过氧自由基化学研究的重点和难点。本文总结了大气过氧自由基实地测量的技术方法,回顾了涉及大气过氧自由基的大型实地观测实验,分析了已有观测实验中大气过氧自由基的浓度水平和差异,归纳了实地测量数据在化学机理研究中的应用,讨论了模拟分析实地测量结果中的主要科学发现。最后,提出该领域中尚存在的问题及可能的重点研究方向。     

对流层中的OH与HO2自由基的研究进展

OH与HO2自由基是大气中重要的氧化剂,研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和了解区域乃至全球大气自净能力有重要意义.自工业革命以来,每年有数千万吨的自然和人为污染物进入对流层,这些物质会严重影响·OH的生成和消除,因此·OH的浓度可能在全球范围内发生大的变化.本文总结了国内外近年来有关·OH与HO2·的最新研究成果,目前比较一致的结论是由于人类活动的影响,全球·OH的浓度比工业革命前降低了.但是在一些污染地区,由于氮氧化合物对·OH的负反馈作用,一定程度上弥补了·OH的净损失.在最近20年中,·OH在对流层中的浓度基本稳定在106cm-3.本文还介绍了实验室研究方法及外场测量技术的进展,提出了尚待解决的一些问题.     

北京地区臭氧污染的来源分析

光化学烟雾污染是影响北京地区夏季空气质量的一个重要环境问题．利用区域空气质量模（CAMx）对2000年6月底至7月初发生在北京地区的臭氧污染过程进行模拟,运用臭氧源识别技术（OSAT）和地区臭氧评估技术（GOAT）,量化了不同地区的污染源排放对北京市城近郊区臭氧污染的贡献,探讨了周边地区排放的臭氧贡献方式问题,分析了北京地区臭氧污染的化学机制特征．研究表明,北京地区臭氧污染分布存在显著差异,并且具有明显的区域性特征,定陵地区的超标臭氧主要受到城近郊区烟羽的严重影响（占55％）,城近郊区则除了受到北京市的前体物排放影响外（占46％）,来自天津市、河北省南部地区的贡献往往也占有重要份额;周边地区对北京市城近郊区的贡献中,直接输入的臭氧约占七层,其余部分以输入前体物的方式贡献臭氧;北京城近郊区的臭氧生成主要受挥发性有机物控制,而在远郊区县和农村地区臭氧生成对氮氧化物变得更为敏感．对北京地区臭氧污染的源排放控制,需要综合考虑各种臭氧来源和不同贡献方式的重要性,以及臭氧生成机制的变化规律．     

HNO2异构体及其相互转化反应机理的量子化学研究

NO在对流层和平流层的光化学过程起重要作用。HO自由基在清除大气污染物和生成臭氧过程中起着关键作用。HO自由基与NO反应生成非常活泼的自由基HONO,这在气相化学中具有重要地位。Cleaner等发现HNO2存在多种异构体,这些异构体间怎样转化以及其能否稳定存在的问题非常重要。     

臭氧加热对大气环流影响的数值试验

本文在一个全球9层大气环流模式中,加入一个臭氧方程来模拟臭氧吸收太阳紫外辐射对高层大气的加热作用以及由此而引起的温、压、风场的变化。试验表明平流层臭氧加热率远大于其它要素,如水汽等引起的加热率。在考虑臭氧加热作用的情况下,计算出的对流层顶以上的温度分布和纬向风强度与不考虑臭氧作用的计算结果有明显差异。臭氧加热作用不仅影响纬向风,同时也影响经向风,因而使Walker环流和Hadley环流都发生相应的变化。试验还表明,臭氧层的存在对各气象要素场的影响在对流层中部已相当小,然而在近地面却还有明显的反应。特别是对陆地上影响比海洋上要强得多。     

硝酰氯的大气化学

硝酰氯(nitryl chloride,ClNO₂)是大气中一种重要的气态污染物,对大气氧化性、一次污染物的降解和二次污染物的生成具有重要影响,并在全球氮循环和氯循环中扮演着不可忽视的角色。本文归纳了ClNO₂的基本物理化学性质及其在大气中的生成和去除机制,并介绍了实验室研究和外场观测中ClNO₂的主要测量方法。在此基础上,本文总结了过去十几年报道的ClNO₂在实际大气中的时空分布特征,通过分析实验室模拟和外场观测的研究结果系统讨论了ClNO₂非均相生成的机制、产率及其影响因素,探讨了ClNO₂对氯自由基、大气氧化性以及臭氧和硝酸盐形成的影响。我们指出,ClNO₂既耦合了气相化学和非均相化学,又耦合了夜间大气化学和日间光化学,在我国大气复合污染中可能起着非常重要的作用。最后,本文提出了ClNO₂大气化学研究中尚待解决的关键科学问题,并简要讨论了该领域的未来发展方向。     

大气“霾化学”:概念提出和研究展望

大气污染是人类面临的重大环境挑战。我国大气污染具有高度的复合污染特征,其形成过程既有高强度的颗粒物均相成核现象,又有多介质非均相致霾过程,同时耦合了强的大气氧化性以及O₃污染,是不同于洛杉矶光化学烟雾和伦敦烟雾的新型“霾化学”烟雾污染。“霾化学”区别于并突破现有的理论认识,是解析我国典型多介质复合污染环境下PM_2.5成因以及PM_2.5与O₃污染间非线性复杂关系,综合研究气、液、固多介质非均相过程的大气污染化学。研究“霾化学”过程对精准控制我国乃至其他国家大气复合污染意义重大。本文提出和总结了大气“霾化学”概念,并对“霾化学”理论的完善和发展进行了展望。     

大气条件下O3与乙炔反应速率常数的测定

O₃是对流层大气中一种重要的氧化剂, 其与反应活性气体的反应是大气对流层中重要的反应过程, 对于研究空气污染的对策有重要意义. 我们使用自行建设的烟雾箱模拟反应装置, 结合O₃分析仪和气相色谱研究了O₃和乙炔的反应. 研究测得O₃和乙炔在室温下(15 ℃)反应的4次实验的速率常数的平均值为4.13×10^－21 cm³•molecule^－1•s^－1, 其变动系数为7%. 与文献中采用其它方法得到的实验值相吻合. 所得结果表明, 我们测定的反应速率常数有较高的精密度, 我们所建的大气反应烟雾箱模拟系统是可靠的, 可以用于大气O₃浓度条件下O₃的其它大气化学反应过程的深入研究, 为进一步深入研究大气中其它重要反应活性气体的化学反应提供了一定的基础.     

Reactive halogen chemistry in the troposphere

Halogen chemistry is well known for ozone destruction in the stratosphere, however reactive halogens also play an important role in the chemistry of the troposphere. In the last two decades, an increasing number of reactive halogen species have been detected in a wide range of environmental conditions from the polar to the tropical troposphere. Growing observational evidence suggests a regional to global relevance of reactive halogens for the oxidising capacity of the troposphere. This critical review summarises our current understanding and uncertainties of the main halogen photochemistry processes, including the current knowledge of the atmospheric impact of halogen chemistry as well as open questions and future research needs.     

Anthropogenic ozone,acids and mutagens: Half a century of Pandora’S Nox

It has been four decades since the phenomenon of photochemical air pollution was first characterized and, in the same year, a tragic London smog episode caused 4,000 excess deaths. Since then, there has been a substantial increase in our understanding of the chemistry involved in both types of air pollution, and a recognition that there is a very close chemical interrelationship between them. In this overview, we provide a brief historical perspective on the atmospheric chemistry of photochemical smog and illustrate how fundamental studies on the gas-phase chemistry of uv-irradiated mixtures of volatile organic compounds (VOC) and oxides of nitrogen (NO_x in polluted laboratory and ambient air masses have contributed to our understanding of three environmental problems: the atmospheric formation of ozone, nitric acid and airborne mutagens. In particular, we demonstrate the central role played by nitrogen dioxide and the hydroxyl radical in each case. We also show how certain reactive toxic and acidic species, e.g., formaldehyde and nitrous and formic acids, have been characterized in smog chambers and ambient smog by long pathlength spectroscopic techniques. It is shown that by using the same methods they now have been identified unequivocally, along with NO₂, in certain common types of polluted indoor atmospheres ... and at much higher concentrations than outdoors. This has significant health implications for indoor HCHO and quite possibly the acids. We then trace the history of the direct mutagenicity of respirable particles in polluted ambient air and show how, through use of the Ames test in biologically-directed assays of products coupled with fundamental studies of gas-phase reactions of polycyclic aromatic hydrocarbons (PAH) and NO_x in irradiated air, much of this activity can be accounted for in terms of the formation of nitro-PAH and oxygenated derivatives. Finally, we discuss the application of basic kinetic, mechanistic and analytical, experimental techniques and theoretical concepts to the development of a new set of “reactivity-based” regulatory controls on motor vehicle emissions of VOC’s. This novel regulatory approach applied by California’s Air Resources Board, which takes effect in 1994, illustrates the continuing need for fundamental research in the area of atmospheric chemistry and how it may be applied to “real world” environmental problems.     

Particle formation and surface processes on atmospheric aerosols: A review of applied quantum chemical calculations

Aerosols significantly influence atmospheric processes such as cloud nucleation, heterogeneous chemistry, and heavy-metal transport in the troposphere. The chemical and physical complexity of atmospheric aerosols results in large uncertainties in their climate and health effects. In this article, we review recent advances in scientific understanding of aerosol processes achieved by the application of quantum chemical calculations. In particular, we emphasize recent work in two areas: new particle formation and heterogeneous processes. Details in quantum chemical methods are provided, elaborating on computational models for prenucleation, secondary organic aerosol formation, and aerosol interface phenomena. Modeling of relative humidity effects, aerosol surfaces, and chemical kinetics of reaction pathways is discussed. Because of their relevance, quantum chemical calculations and field and laboratory experiments are compared. In addition to describing the atmospheric relevance of the computational models, this article also presents future challenges in quantum chemical calculations applied to aerosols.     

Spectroscopic measurement of the free radicals NO3, BRO,IO, and OH in the troposphere

Free radicals are the driving force for most chemical processes in the atmosphere. In particular OH- and nitrate radicals (NO₃) play a central role in the troposphere. However, recent investigations indicate an important influence of the halogen-oxide radicals BrO, IO, and possibly ClO on tropospheric chemistry. Therefore, the knowledge of the concentration of those species in the atmosphere is a key requirement for the investigation of atmospheric chemistry. Unfortunately the low concentration of free radicals makes measurements particularly difficult. Among several techniques applied to the problem UV/visible differential absorption spectroscopy (also known as DOAS) appears to be the most successful for the observation of the above species. Detection limits of the order of 10⁶ to 10⁷ molec/cm³ have been reached, which are sufficiently low to resolve the diurnal variation profiles of the observed radicals. As examples tropospheric DOAS measurements of NO₃- and OH radicals at mid latitudes are presented, as well as observations of BrO in the Canadian Arctic. The latter measurements are discussed with a scenario combining BrO catalyzed ozone loss and atmospheric dispersion to explain the observed rapid changes in ozone with the measured levels of BrO.     

Problems connected with the analysis of halocarbons and hydrocarbons in the non-urban atmosphere

The problems connected with the measurement of hydrocarbons outside urban areas are considerable: The atmospheric mixing ratios of most of the hydrocarbons are very low--from a few ppb down to some ppt; the mixture of hydrocarbons is extremely complex, ranging from light n-alkanes to alkyl benzenes and terpenes; for measurements in remote areas the logistic conditions often restrict the instrumentation which can be used for sample collection or in situ measurements (such as lack of electric power supply, weight restrictions etc.). Nevertheless, sensitive and sufficiently reliable measurements of hydrocarbons in the non-urban atmosphere are important. Hydrocarbons are important factors in the tropospheric photochemistry (e.g. ozone formation) and can be used as valuable tracers for man-made atmospheric pollutants etc. Other useful tracers for anthropogenic emission are halocarbons such as dichlormethane, tri- and tetrachloroethen etc. The impact of man-made hydrocarbons on the chemistry of the troposphere can only be understood if the extent of natural (biogenic) contributions is known. From measurements of a large variety of hydrocarbons and halocarbons it is often possible to obtain information about the sources of the most important atmospheric hydrocarbon species, even for trace gases with both significant anthropogenic and biogenic sources. In this presentation some of the problems and their solutions connected with such measurements of atmospheric hydrocarbons and halocarbons are presented and discussed. Some of the results obtained by several series of measurements are described, indicating that man-made as well as biogenic hydrocarbons can be important factors for the chemistry of the atmosphere.     

Global inorganic source of atmospheric bromine

A few bromine molecules per trillion (ppt) causes the complete destruction of ozone in the lower troposphere during polar spring and about half of the losses associated with the "ozone hole" in the stratosphere. Recent field and aerial measurements of the proxy BrO in the free troposphere suggest an even more pervasive global role for bromine. Models, which quantify ozone trends by assuming atmospheric inorganic bromine (Bry) stems exclusively from long-lived bromoalkane gases, significantly underpredict BrO measurements. This discrepancy effectively implies a ubiquitous tropospheric background level of approximately 4 ppt Bry of unknown origin. Here, we report that I- efficiently catalyzes the oxidation of Br- and Cl- in aqueous nanodroplets exposed to ozone, the everpresent atmospheric oxidizer, under conditions resembling those encountered in marine aerosols. Br- and Cl-, which are rather unreactive toward O3 and were previously deemed unlikely direct precursors of atmospheric halogens, are readily converted into IBr2- and ICl2- en route to Br2(g) and Cl2(g) in the presence of I-. Fine sea salt aerosol particles, which are predictably and demonstrably enriched in I- and Br-, are thus expected to globally release photoactive halogen compounds into the atmosphere, even in the absence of sunlight.     

TNO Institute of Environmental Sciences, Energy Research and Process Innovation, the Netherlands

Abstract— A radiative transfer model is used to study the effect of stratospheric ozone depletion and tropospheric pollution on UVB (280-315 nm) radiation in the troposphere at midiatitudes of the Northern Hemisphere. The difference in the vertical distribution of UVB radiation for a range of pollution conditions typical for remote clean and more polluted sites on cloudless summer days is shown. The changes in downward UVB irradiance, UVB actinic flux, DNA-weighted UV radiation and photodissociation frequency of ozone at the earth's surface are quantified in relation to stratospheric ozone depletion and typical ranges of tropospheric pollutants (ozone [O3], sulfur dioxide [SO₂] and aerosols) in nonurban polluted regions. The results show that near the earth's surface, in non-urban polluted regions, an increase of tropospheric pollution, which occurred over the last 50-100 years, has cancelled the effect of an increase of UVB radiation due to stratospheric ozone depletion that has occurred since the late 1970s. The results hold for summer conditions and the decrease of UVB radiation is most pronounced in the polluted boundary layer. At higher altitudes the effect of tropospheric pollution on UVB radiation is far less. Prior to 1970 it was mainly tropospheric pollution that altered UVB radiation at the surface of the earth. In addition, since the late 1970s enhanced UVB radiation reaching the top of the troposphere, due to stratospheric ozone depletion, also had an impact on UVB levels in the troposphere.