大气中挥发性有机化合物与氮氧化物的反应研究
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摘要
大气环境污染尤其是气溶胶污染,因污染物组成成分复杂、影响因素繁多、涉及范围广泛以及研究治理难度大等特点,是一个突出的环境问题,也是环境科学研究的热点问题。气溶胶中的二次有机气溶胶SOA多数属于PM2_5,除了能引起大气光化学烟雾和酸沉降,影响大气的能见度和区域气候以外,还含有多种毒性很强的有机物,会对生态系统和人类健康造成严重威胁。SOA是全球大气中气溶胶的主要贡献者,而其主要来源于可挥发性有机化合物VOCs(主要包括生物源排放的挥发性有机化合物BVOCs和人为源排放的挥发性有机化合物AVOCs)发生氧化或光氧化反应形成。
VOCs性质活泼,能参与大气中的多种化学和光化学反应,从而影响大气成分、污染物的转化、区域大气质量、区域气候变化等。大气BVOCs的最主要组成是异戊二烯,而环氧化合物是异戊二烯形成SOA过程中的重要中间体。因此,环氧化合物的大气化学反应研究成为了当前大气环境领域的一个前沿问题。
本文通过大量细致的实验,深入研究了大气中VOCs形成SOA的反应机制；探讨了某些SOA的前体物与大气中氮氧化物的化学反应。主要研究结果如下：
(1)采用两种方法合成了9种有代表性的BVOCs衍生的环氧化合物,分别研究了这些环氧化合物与NO2在水相、气相和有机相中的反应,并进行了相关的动力学和反应机理研究,证实了一条由环氧化物进一步形成SOA的可能的新途径。实验结果表明,这些环氧化合物与N02在水相、气相和有机相中反应均形成了相应的有机硝酸酯类物质,后者被证明是SOA的组分；环氧化物除了可与无机硝酸盐和硝酸反应形成SOA组分,还可以直接与N02反应形成。动力学研究结果表明,在N02浓度相对较高的情况下,环氧化物与N02的反应可看作一级反应,线性拟合符合一级动力学曲线。反应机理研究结果表明,NO2与环氧化合物的反应生成有机硝酸酯,很有可能是一种自由基历程。
(2)研究了城市大气SOA的重要AVOCs前体物芳香族化合物与NO2的化学及光化学反应。首先制备了8种具有代表性的芳烃化合物,将其分别在无光照和光照射下与N02进行气相反应。反应产物均通过色谱分析进行了鉴定,研究了反应机理。结果表明,芳烃化合物在无光照和光照射条件下,均能与NO2进行气相反应生成硝基苯类化合物。这一系列实验证实了,环境中的硝基苯类化合物不仅可以通过工业生产排放产生,还可通过大气中挥发性有机芳烃化合物与NO2直接发生自由基反应产生。
(3)合成了7种具有代表性的芳烃化合物,将其分别在无光照和光照射条件下与NO进行气相反应,反应产物通过多种测试仪器进行了分析鉴定,进行了机理研究。结果表明,芳烃化合物在无光照和光照射条件下,与NO气体反应,均生成相应的硝基苯类化合物。结果证实了大气环境中的硝基苯类化合物的一条新的产生途径,即可通过大气中挥发性有机芳烃化合物与大气NO直接发生自由基反应或者单电子转移反应产生。
The atmospheric environmental pollution, especially the aerosol pollution has long been an elusive topic for scientists. It is very difficult to be resolved due to its features such as complexity of pollutant, variety of the influence factors, wide range, and difficulty of control etc. Among the aerosol, the secondary organic aerosol (SOA) is very important and most of them are PM2.5, which can pose grave threat to ecosystem and mankind because the SOA can not only cause atmospheric photochemical smog and acid deposition affecting visibility and regional climate, but also contain various highly toxic organic compounds. The SOA is the main contribution of the aerosol in global atmosphere. It can be formed by oxidation or photooxidation of biogenic and anthropogenic volatile organic compounds (BVOCs,AVOCs) in the atmospheric environment.
In the first part of this thesis, some concepts, research background, the concerned developments as well as the research significance and novelty of this work have been described here. The aerosol, SOA and its generation mechanism as well as the VOCs including its category, origin, and harms are also depicted in details. Although VOCs are only trace gas in the atmosphere, the studies on the VOCs play a great role in the field of atmospheric chemistry. Most of the VOCs are so active enough to be involved in a variety of chemical and photochemical reactions. As a result, the derivatives and products from VOCs thus affect many aspects such as the component of air, transformation of pollutant, regional atmospheric quality and change of regional climate. Therefore, the investigation on the atmospheric chemistry and photochemistry of VOCs has long been the research focus of scientists. It is well known that the isoprene is the most important BVOCs in air. Recent studies show that the epoxide is the key intermediate in the process of SOA formation from isoprene. It is believed that the formation of epoxide is very important to investigate the mechanism for the SOA formation via isoprene. Hence, the research on the atmospheric chemistry and photochemistry of epoxide has become a new hotspot in the current field of atmospheric chemistry.
In the secondary, the third and the fourth part of this thesis, the main experimental studies have been demonstrated in details. The mechanism for SOA formation via VOCs in air has been investigated extensively through a series of carefully designed experiments. Additionally, the chemical reactions of some precursors of SOA with nitric oxides in atmosphere have also been studied. The details for the corresponding experimental methods, procedures and the conclusions have been described as following.
(1) Nine epoxides represented the typical derivatives of BVOCs have been prepared by using two different methods. The reactions of epoxides with nitrogen dioxide (NO2) in water, gas phase and organic phase have been carried out respectively. In addition, the reaction kinetics and mechanism have also been investigated extensively. The results indicate that the corresponding organic nitrates have been obtained by the reactions of epoxides with NO2in water, gas phase and organic medium, and the organic nitrates have been proved to be component of SOA. As a result, these experiments find a novel possible process of SOA formation from epoxide. The results also suggest that organic nitrates in atmosphere can be formed directly by reactions of epoxides with NO2apart from reaction of epoxide with inorganic nitrate and nitric acid, which is well known before. In addition, the kinetics studies indicate that the reaction of epoxide with NO2can be considered as first order reaction under the conditions of high NO2concentration, and the linear fitting results also fit the first order kinetics curve well. Finally, the mechanistic studies suggest that the reaction of NO2with epoxide most likely proceeds via a free radical process.
(2) The chemical and photochemical reactions of NO2with a large class of important AVOCs arenes derived from city atmospheric SOA have been carried out in this part. Eight representative arenes have been synthesized and the gas phase reactions of these compounds with NO2with and/or without light irradiation have also been investigated. All of the products have been determined by chromatography and the possible mechanism has also been studied. The results indicate that a series of nitrobenzenes have been formed by gas phase reactions of arenes with NO2under or not light irradiation. Therefore, a conclusion can be drawn out that the nitrobenzenes in air and environment are produced not only by anthropogenic emissions from chemical industry, but also by direct radical reaction of NO2with these volatile organic arenes.
(3) In the fourth part, seven representative arenes have been prepared. Additionally, with or without light irradiation, the reactions of nitric oxide (NO) with these compounds in gas phase have been carried out. Furthermore, careful analysis of the results as well as the mechanism has also been done. Similarly, the results show that various nitrobenzenes have also been obtained by the gas phase reactions of NO with arenes under light irradiation or not, which confirm a new process of nitrobenzene formation in atmosphere and environment. This means that these hazardous nitrobenzene derivatives not only come from chemical industry emissions, but also can be generated by direct radical or single electron transfer reactions of NO with atmospheric volatile organic aromatic compounds.
Finally, the author summarizes all of the experiments, methods, results and conclusions. In addition, the continuous work plan and blueprint in the future have also been drawn out at the end of this thesis.
VOCs性质活泼,能参与大气中的多种化学和光化学反应,从而影响大气成分、污染物的转化、区域大气质量、区域气候变化等。大气BVOCs的最主要组成是异戊二烯,而环氧化合物是异戊二烯形成SOA过程中的重要中间体。因此,环氧化合物的大气化学反应研究成为了当前大气环境领域的一个前沿问题。
本文通过大量细致的实验,深入研究了大气中VOCs形成SOA的反应机制；探讨了某些SOA的前体物与大气中氮氧化物的化学反应。主要研究结果如下：
(1)采用两种方法合成了9种有代表性的BVOCs衍生的环氧化合物,分别研究了这些环氧化合物与NO2在水相、气相和有机相中的反应,并进行了相关的动力学和反应机理研究,证实了一条由环氧化物进一步形成SOA的可能的新途径。实验结果表明,这些环氧化合物与N02在水相、气相和有机相中反应均形成了相应的有机硝酸酯类物质,后者被证明是SOA的组分；环氧化物除了可与无机硝酸盐和硝酸反应形成SOA组分,还可以直接与N02反应形成。动力学研究结果表明,在N02浓度相对较高的情况下,环氧化物与N02的反应可看作一级反应,线性拟合符合一级动力学曲线。反应机理研究结果表明,NO2与环氧化合物的反应生成有机硝酸酯,很有可能是一种自由基历程。
(2)研究了城市大气SOA的重要AVOCs前体物芳香族化合物与NO2的化学及光化学反应。首先制备了8种具有代表性的芳烃化合物,将其分别在无光照和光照射下与N02进行气相反应。反应产物均通过色谱分析进行了鉴定,研究了反应机理。结果表明,芳烃化合物在无光照和光照射条件下,均能与NO2进行气相反应生成硝基苯类化合物。这一系列实验证实了,环境中的硝基苯类化合物不仅可以通过工业生产排放产生,还可通过大气中挥发性有机芳烃化合物与NO2直接发生自由基反应产生。
(3)合成了7种具有代表性的芳烃化合物,将其分别在无光照和光照射条件下与NO进行气相反应,反应产物通过多种测试仪器进行了分析鉴定,进行了机理研究。结果表明,芳烃化合物在无光照和光照射条件下,与NO气体反应,均生成相应的硝基苯类化合物。结果证实了大气环境中的硝基苯类化合物的一条新的产生途径,即可通过大气中挥发性有机芳烃化合物与大气NO直接发生自由基反应或者单电子转移反应产生。
The atmospheric environmental pollution, especially the aerosol pollution has long been an elusive topic for scientists. It is very difficult to be resolved due to its features such as complexity of pollutant, variety of the influence factors, wide range, and difficulty of control etc. Among the aerosol, the secondary organic aerosol (SOA) is very important and most of them are PM2.5, which can pose grave threat to ecosystem and mankind because the SOA can not only cause atmospheric photochemical smog and acid deposition affecting visibility and regional climate, but also contain various highly toxic organic compounds. The SOA is the main contribution of the aerosol in global atmosphere. It can be formed by oxidation or photooxidation of biogenic and anthropogenic volatile organic compounds (BVOCs,AVOCs) in the atmospheric environment.
In the first part of this thesis, some concepts, research background, the concerned developments as well as the research significance and novelty of this work have been described here. The aerosol, SOA and its generation mechanism as well as the VOCs including its category, origin, and harms are also depicted in details. Although VOCs are only trace gas in the atmosphere, the studies on the VOCs play a great role in the field of atmospheric chemistry. Most of the VOCs are so active enough to be involved in a variety of chemical and photochemical reactions. As a result, the derivatives and products from VOCs thus affect many aspects such as the component of air, transformation of pollutant, regional atmospheric quality and change of regional climate. Therefore, the investigation on the atmospheric chemistry and photochemistry of VOCs has long been the research focus of scientists. It is well known that the isoprene is the most important BVOCs in air. Recent studies show that the epoxide is the key intermediate in the process of SOA formation from isoprene. It is believed that the formation of epoxide is very important to investigate the mechanism for the SOA formation via isoprene. Hence, the research on the atmospheric chemistry and photochemistry of epoxide has become a new hotspot in the current field of atmospheric chemistry.
In the secondary, the third and the fourth part of this thesis, the main experimental studies have been demonstrated in details. The mechanism for SOA formation via VOCs in air has been investigated extensively through a series of carefully designed experiments. Additionally, the chemical reactions of some precursors of SOA with nitric oxides in atmosphere have also been studied. The details for the corresponding experimental methods, procedures and the conclusions have been described as following.
(1) Nine epoxides represented the typical derivatives of BVOCs have been prepared by using two different methods. The reactions of epoxides with nitrogen dioxide (NO2) in water, gas phase and organic phase have been carried out respectively. In addition, the reaction kinetics and mechanism have also been investigated extensively. The results indicate that the corresponding organic nitrates have been obtained by the reactions of epoxides with NO2in water, gas phase and organic medium, and the organic nitrates have been proved to be component of SOA. As a result, these experiments find a novel possible process of SOA formation from epoxide. The results also suggest that organic nitrates in atmosphere can be formed directly by reactions of epoxides with NO2apart from reaction of epoxide with inorganic nitrate and nitric acid, which is well known before. In addition, the kinetics studies indicate that the reaction of epoxide with NO2can be considered as first order reaction under the conditions of high NO2concentration, and the linear fitting results also fit the first order kinetics curve well. Finally, the mechanistic studies suggest that the reaction of NO2with epoxide most likely proceeds via a free radical process.
(2) The chemical and photochemical reactions of NO2with a large class of important AVOCs arenes derived from city atmospheric SOA have been carried out in this part. Eight representative arenes have been synthesized and the gas phase reactions of these compounds with NO2with and/or without light irradiation have also been investigated. All of the products have been determined by chromatography and the possible mechanism has also been studied. The results indicate that a series of nitrobenzenes have been formed by gas phase reactions of arenes with NO2under or not light irradiation. Therefore, a conclusion can be drawn out that the nitrobenzenes in air and environment are produced not only by anthropogenic emissions from chemical industry, but also by direct radical reaction of NO2with these volatile organic arenes.
(3) In the fourth part, seven representative arenes have been prepared. Additionally, with or without light irradiation, the reactions of nitric oxide (NO) with these compounds in gas phase have been carried out. Furthermore, careful analysis of the results as well as the mechanism has also been done. Similarly, the results show that various nitrobenzenes have also been obtained by the gas phase reactions of NO with arenes under light irradiation or not, which confirm a new process of nitrobenzene formation in atmosphere and environment. This means that these hazardous nitrobenzene derivatives not only come from chemical industry emissions, but also can be generated by direct radical or single electron transfer reactions of NO with atmospheric volatile organic aromatic compounds.
Finally, the author summarizes all of the experiments, methods, results and conclusions. In addition, the continuous work plan and blueprint in the future have also been drawn out at the end of this thesis.
引文
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