首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons   总被引：15，自引：0，他引：15  
Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO3 reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.  相似文献   

2.
Five aromatic hydrocarbons – benzene, toluene, ethylbenzene, p-xylene and 1,2,4-trimethylbenzene – were selected to investigate the laser desorption/ionization mass spectra of secondary organic aerosols (SOA) resulting from OH-initiated photooxidation of aromatic compounds. The experiments were conducted by irradiating aromatic hydrocarbon/CH3ONO/NO X mixtures in a home-made smog chamber. The aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the aerodynamic size and chemical composition of individual secondary organic aerosol particles in real-time. Experimental results showed that aerosol created by aromatics photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and different aromatic hydrocarbons SOA mass spectra have eight same positive laser desorption/ionization mass spectra peaks: m/z = 18, 29, 43, 44, 46, 57, 67, 77. These mass spectra peaks may come from the fragment ions of the SOA products: oxo-carboxylic acids, aldehydes and ketones, nitrogenated organic compounds, furanoid and aromatic compounds. The possible reaction mechanisms leading to these products were also discussed.  相似文献   

3.
Global secondary organic aerosol formation (SOA) is currently assumed to be between 11.2 and 270 Tg/yr. This range of uncertainty is reflected in the gas-phase chemistry. In this study, we focus on the feedback of SOA formation on the concentrations of most important trace gases such as ozone, and compare it to the impact of monoterpene gas-phase chemistry with a newly developed reduced monoterpene mechanism (MMM) for either α- or β-pinene in the global chemistry transport model MATCH-MPIC. With this set-up an uncertainty range of 3.5–4.0% increase in annually averaged tropospheric ozone was found to be caused by the gas-phase chemistry of the investigated monoterpenes. Moreover, a strong feedback has been observed for NOx, HCHO, HNO3 and PAN. These observations are affected remarkably by different SOA formation approaches like partitioning or saturation vapour pressure limitation and by the structure of the monoterpene used, e.g. reducing the impact on tropospheric ozone to 1.2–1.9% by using the partitioning approach versus the simulation with gas-phase chemistry only. Therefore, a consideration of the individual processes associated with SOA formation seems to be necessary to reduce the uncertainty in SOA formation and to understand the impact of VOCs on atmospheric chemistry. An erratum to this article is available at .  相似文献   

4.
Construction and characterization of an atmospheric simulation smog chamber   总被引：11，自引：0，他引：11  
Currently, air pollution in Beijing has become a complex problem with two types of source pollutants： coal smoke and photochemical smog. Furthermore the maximum hourly mean concentration of O3 increases continuously, especially in the summer. In order to simulate the photochemical reaction, develop an air quality simulation model and further improve the air quality of Beijing, a precisely temperature-controlled, indoor, smog chamber facility was designed and constructed at Tsinghua University. Characterization experiments have been carried out to acquire the basic parameters of the smog chamber, such as the wall loss rates of NO2, NO, O3, C3H6 and particulate matter （PM）, the intensity of ultraviolet （UV） light in the chamber, the reactivity of the purified air and the reproducibility of the experimental results. The results indicate that the facility performs up to specifications, and can meet the demands required for simulating the photochemical reaction. The effect of high primary contaminated PM on the formation of ozone and secondary organic aerosol （SOA） is under investigation.  相似文献   

5.
The gas-particle partitioning of select semivolatile organic compounds (SOCs) was studied by injecting the SOCs into a 190 m3 Teflon film chamber containing a secondary organic aerosol (SOA) generated by volatilizing liquid -pinene into an ozone-concentrated atmosphere. The concentration of total suspended particulates (TSP) and gas and particle-phase SOCs was measured over the course of three experiments spanning a temperature range of 268–297 K and a relative humidity range of 55–100%. An equilibrium partition coefficient, Kp, was calculated for each sampling event. Empirical relationships were then developed to predict the partitioning of the SOCs on the SOA particle source as a function of temperature. Partitioning in this SOA system was compared to that of a SOA generated by the photochemical reaction of NOx with m-xylene. The results indicate that partitioning is similar between the two SOA systems. The effects of multiple particle sources on partitioning was also examined, revealing that a weighted average of predicted Kp values for individual sources can be used to predict partitioning in aerosol mixtures.  相似文献   

6.
  相似文献   

7.
Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: -pinene, -pinene, 3-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O3 reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for -pinene, sabinene, -pinene, and 3-carene, respectively. The identified individual products account for >83%, 100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of -pinene, sabinene, -pinene, and 3-carene. The uncertainty in the yield data is estimated to be ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.  相似文献   

8.
The gas and particle phase products from the reaction of -pinene with the atmospheric oxidants O3 and OH radicals in the presence of NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of -pinene in the presence of O3/air and the daytime oxidation of -pinene in the presence of NOx/air and natural sunlight were carried out in the University of North Carolina large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. A Scanning Mobility Particle Sizer system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study the secondary organic aerosol (SOA) formation, and a filter pack/denuder sampling system was used for simultaneously collecting gas and particle phase products for analysis. A gas chromatograph coupled to a mass spectrometer (GC-EIMS or GC-CIMS) was used for the identification and quantification of gas and aerosol products. A HPLC method was used for the measurement of small carbonyl compounds (aldehydes and ketones) as their 2,4-dinitrophenylhydrazones (DNPH) derivatives. Mass balances for gaseous and aerosol reaction products were reported over the course of the reaction. More than sixteen products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 57 to 71% of the reacted -pinene carbon. Measurements showed that a number of reaction products were found in both O3 and NOx systems (pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxynopinone, 3-hydroxynopinone, and nopinone). Pinic acid, pinalic-3-acid, and 4-hydroxypinalic-3-acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols. Detailed reaction schemes are presented to account for most of the observed reaction products.  相似文献   

9.
The amounts of SOA and reactive oxygen species (ROS) formed by the reaction of α-pinene with ozone (O3) in the presence of nitric oxide (NO) were studied by varying the ratio of O3 to NO in a chamber under conditions that simulate the indoor environment. The particle mass was measured using a tapered element oscillating microbalance (TEOM) and a scanning mobility particle sizer (SMPS) was used to obtain particle volume distributions. The concentrations of particle-bound reactive species (ROS) were quantitatively determined from collected filters by the measuring the oxidation of dichlorofluorescin (DCFH) to a fluorescent product. The measured fluorescent intensities were converted to equivalent H2O2 concentrations. Three sets of experiments using different concentration ratios of NO/O3 were conducted. Measured steady-state, particle-bound ROS concentrations ranged from 0.58 to 6.78 nmol/m3 of H2O2. The SOA yields were examined using Odum’s SOA yield model that relates the mass of SOA formed to the mass of hydrocarbon consumed. For the condition where NO and O3 were in a concentration ratio of 0.5, the SOA yield was the highest with 22 % of α-pinene converted to SOA. Under these experimental conditions, the highest concentration of nitrate radical in these experiments would have been produced.  相似文献   

10.
In the last decade, numerous studies of monoterpene hydrocarbons in the presence of ozone and oxides of nitrogen have been completed. Although insights about the reactivity of terpenes have been gained, and several products have been identified in the gas and aerosol phases, carbon balances have been generally poor. This paper describes a radiotracer technique which accounts for carbon-containing compounds in a smog chamber at the conclusion of a photooxidation or ozonolysis reaction. Instead of attempting to identify individual products, gas-phase compounds were separated from aerosols, and each phase was analyzed by a liquid scintillation counter. A carbon balance of 79 to 97% was obtained with 14C--pinene and ozone using this technique. The significance of the results are discussed in terms of the 14C--pinene concentrations used in this study, which were lower than concentrations used previously by one to four orders of magnitude. In spite of the lower concentrations, the gaseous and aerosol fractions observed in the present investigation are comparable to those observed by others. Possible reaction products are discussed with respect to likely mechanisms for -pinene oxidation.  相似文献   

11.
Nitrogen-containing organic compounds (NOC) formed from secondary organic aerosols (SOA) age via reaction with reduced nitrogen species are a vital class of brown carbon compounds. NOC compounds from ammonia (NH3) gas-aging of benzene SOA were investigated in present study, and the experiments were performed by irradiating benzene/CH3ONO/NO/NH3 air mixtures in a home-made smog chamber. The particulate NOC products of aged benzene SOA in the presence of NH3 were measured by UV-Vis spectrophotometer, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm, respectively. Experimental results demonstrated that NH3 has significant promotion effect on benzene SOA formation. Organic ammonium salts, such as ammonium glyoxylate, ammonium 6-oxo-2,4-hexadienoiclate, which are formed from NH3 reactions with gaseous organic acids were detected as the major particulate NOC products of NH3-aged benzene SOA. 1H–imidazole, 1H–imidazole-2-carbaldehyde and other imidazole products via the heterogeneous reactions between NH3 and dialdehydes of benzene SOA were successfully detected as important brown carbon constituents. The formation of imidazole products suggests that some ambient particles contained organonitrogen compounds may be come from this mechanism. The results of this study may provide valuable information for discussing NH3 deposition and SOA aging mechanisms.  相似文献   

12.
Outdoor smog chamber experiments were performed to investigate gas/particle (G/P) partitioning behavior of aldehyde compounds in atmospheric acidic aerosols. Diesel soot and wood smoke aerosols were selected as acidic aerosols and octanal, decanal, undecanal, and cis-pinonaldehyde for aldehydes compounds. Aerosol acidity was measured with the equivalent sulfuric acid amounts in aerosol mass: 0.2–0.6 wt% in diesel soot and 0.04–0.1 wt% in wood smoke aerosols. Experimentally determined partitioning coefficients of aldehyde along with other classes of semivolatile organic compounds (SOCs) were compared with the estimation. All experimental G/P partitioning coefficients of aldehyde compounds were 10–200 times higher than estimated partitioning coefficients. Aldehyde partitioning coefficients in wood soot were similar or less than diesel soot aerosols.  相似文献   

13.
实验室模拟研究大气二次有机气溶胶的形成   总被引：1，自引：0，他引：1  
徐永福  贾龙 《大气科学》2018,42(4):767-785
二次有机气溶胶（SOA）是大气中重要的气溶胶组分,主要由挥发性有机物（VOCs）经化学转化形成,对天气、气候、大气环境和人体健康有重要影响,但至今其确切的化学成分和形成机制还十分不清楚。研究SOA的方法主要采用实验室单个物种或多物种的化学过程的模拟研究,野外实际大气的SOA化学成分、源汇和多尺度分析的观测研究,以及大气中SOA形成的数值模拟的回报和预报研究。实验室研究是对SOA形成过程中获取基础数据和推究SOA生成机制的最主要手段。在过去的几十年中,特别是近五年,SOA的研究取得了较大的进展,其中包括SOA前体物、SOA形成机制及影响因子的进一步理解。本文就这些方面展开了概要性的综述,重点强调了我国研究人员所做的研究工作。在采用实验室烟雾箱系统模拟研究SOA方面,首先简述了烟雾系统的发展以及表征,讨论了跟烟雾箱箱体相关的壁效应问题,重点综述了萜烯类、芳香烃类、小分子类等化学物种转化形成SOA的研究进展。在采用流动管和其他反应器类模拟研究SOA方面,重点讨论了挥发性有机物在颗粒物表面或在液相中所形成的SOA的主要化学成分及其可能的作用。  相似文献   

14.
The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O3 and OH/NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O3/air, and the daytime oxidation of a mixture of -pinene + -pinene with NOx air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O3 and NOx system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.  相似文献   

15.
Organic aerosol formation resulting from the ozonolysis of α-pinene, myrcene and sabinene was investigated in a large aerosol chamber in the presence of aqueous seed aerosols. The chemical composition of the particles was monitored by an aerosol mass spectrometer (Aerodyne Research Inc.) as a function of time and the particle size. Smaller particles were found to contain more organics relative to sulfate than the larger ones. In contrast, the water to sulfate mass ratio was not dependent on the particle size. These experimental findings indicate the formation of organic layers on the particles. With the aid of an aerosol dynamic model we demonstrate that the observations are consistent with the formation of multilayered organic films having thicknesses of approximately 10 nm. The results also suggest that the films were formed through condensation of low-volatile oxidation products that did not take up water considerably. Even though dissolution of oxidation products into the particle aqueous phase cannot be conclusively ruled out, the most plausible interpretation of the results is that the monoterpene ozonolysis lead to the formation of organic coatings on aqueous aerosols. Such films are likely to form in regions with monoterpene emissions.  相似文献   

16.
A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NOx/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a ZefluorTM filter. Oxidation products in the filter extracts were treated using O-(2,3,4,5,6,-pentafluorobenzyl)-hydroxylamine (PFBHA) to derivatize carbonyl groups followed by treatment with N,O-Bis(trimethylsilyl)-acetamide (BSTFA) to derivatize OH groups. The derivatized products were detected with a positive chemical ionization (CI) gas chromatography ion trap mass spectroscopy (GC-ITMS) system. The results of the GC-ITMS analyses were consistent with the previous studies that demonstrated the formation of multi-functional oxygenates. Denuder results showed that many of these same compounds were present in the gas, as well as, the particle phase. Moreover, evidence was found for a series of multifunctional acids produced as higher order oxidation products of the toluene/NOx system. Products having nearly the same mass spectrumwere also found in the ambient environment using identical analytical techniques. These products having multiple acid and alcoholic-OH moieties have substantially lower volatility than previously reported SOA products of the toluene photooxidation and might serve as an indicator for aromatic oxidation in the ambient atmosphere.  相似文献   

17.
Daily measurements of atmospheric aerosol characteristics were carried out in Dolgoprudny (Moscow region) in June–August 2010. The particle concentrations at 11 size gradations within the range of 0.01–10 μm and the concentrations of cloud condensation nuclei active at water vapor supersaturation of 0.2–1% were determined. It is shown that the long anticyclonic conditions and the burning of forests and peat bogs resulted in the increase in total aerosol concentration in surface air by more than 1.5 times and in concentrations of particles with the diameter of 0.1–1 μm and > 1 μm by 5 and 10 times, respectively. The fire smoke mainly consisted of the particles with the size of 0.1–3 μm. The particles with the size of more than 5 μm were not observed. The recurrent visibility decrease up to hundreds of meters was caused by the increase in the concentration of particles with the diameter of more than 0.32μm in the air. During the smoke blanketing, the concentration of active condensation nuclei in aerosol increased almost by 20 times that created an opportunity for watering of aerosol particles and formation of the acid smog.  相似文献   

18.
气溶胶辐射效应在华东地区一次雾霾过程中的作用   总被引：3，自引：1，他引：2  
张悦  樊曙先  李皓  康博识 《气象学报》2016,74(3):465-478
利用WRF/Chem(Weather Research and Forecasting Model coupled with Chemistry)模拟了2013年12月华东地区一次雾、霾事件气溶胶辐射反馈效应对气象场和大气质量的影响。通过3个不同气溶胶浓度设置的试验区分气溶胶浓度不同辐射效应的影响。比较不同试验得出,本次雾、霾过程中,不论是气溶胶直接、半直接辐射效应还是间接效应均使污染地区短波辐射减少、2 m气温下降、大气边界层高度降低,不利于水汽与污染物的扩散,空气污染进一步加重,雾结构进一步稳定,并使雾的持续时间延长,发展高度更高;对于化学场来说,气溶胶直接、半直接辐射效应使污染地区PM_(2.5)浓度增大、消光系数增大、氮氧化物浓度增大,臭氧浓度降低;间接辐射效应使PM_(2.5)浓度和消光系数进一步增大,氮氧化物、臭氧浓度降低。综上所述,气溶胶辐射效应能使大气污染加重,并利于雾的发生、发展。  相似文献   

19.
Anthropogenic emissions alter biogenic secondary organic aerosol(SOA) formation from naturally emitted volatile organic compounds(BVOCs). We review the major laboratory and field findings with regard to effects of anthropogenic pollutants(NOx, anthropogenic aerosols, SO_2, NH_3) on biogenic SOA formation. NOx participate in BVOC oxidation through changing the radical chemistry and oxidation capacity, leading to a complex SOA composition and yield sensitivity towards NOx level for different or even specific hydrocarbon precursors. Anthropogenic aerosols act as an important intermedium for gas–particle partitioning and particle-phase reactions, processes of which are influenced by the particle phase state, acidity, water content and thus associated with biogenic SOA mass accumulation. SO_2 modifies biogenic SOA formation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzed heterogeneous reactions. Some new SO_2-involved mechanisms for organosulfate formation have also been proposed.NH_3/amines, as the most prevalent base species in the atmosphere, influence biogenic SOA composition and modify the optical properties of SOA. The response of SOA formation behavior to these anthropogenic pollutants varies among different BVOCs precursors. Investigations on anthropogenic–biogenic interactions in some areas of China that are simultaneously influenced by anthropogenic and biogenic emissions are summarized. Based on this review, some recommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution to the total SOA budget. This study also highlights the importance of controlling anthropogenic pollutant emissions with effective pollutant mitigation policies to reduce regional and global biogenic SOA formation.  相似文献   

20.
The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10–12 cm3 s–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10–17 cm3 s–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号