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1.
A series of 24 chemical mechanisms from the literature are compared against each other using harmonized emissions, photolysis rate coefficients for simple inorganic chemistry and life cycle data for ozone, PAN and H2O2. The evaluation sought to understand the impact of parameterizing hydrocarbon oxidation on the peak concentrations of photochemically-generated secondary pollutants. Only seven of the 24 chemical mechanisms gave peak concentrations of ozone, PAN and H2O2 simultaneously in their respective central ranges. PAN and H2O2 were generally calculated with a much lower precision compared to ozone. Only 11 mechanisms out of 24 gave responses to both 50% hydrocarbons and NOx emissions controls in their respective central bands. The lack of coordinated ozone, PAN and hydrogen peroxide measurements across Europe currently limits the adequacy of model comparisons and hence the confidence which may be placed in assessments of likely impacts of future control strategies.  相似文献   

2.
The impact of the nocturnal boundary layer (NBL) on the concentrations of O3, H2O2, PAN and CH2O has been studied for two 4-day periods, one in the summer of 1989 and the other in the spring of 1990. Where the presence of the nocturnal layer is clear, O3, PAN and CH2O concentrations decrease rapidly and these species appear to be deposited to the surface. Break-up of the inversion in the morning returns concentrations to levels typical of the previous day. H2O2 is removed much faster than the other species and it is replenished much more slowly. This appears to be due to the H2O2 dissolving in water droplets resulting from the rapid cooling of the air. There is evidence for a morning maximum in PAN, likely due to the combination of high concentrations being brought downwards during the break-up of the NBL followed by thermal decomposition.  相似文献   

3.
邹宇  邓雪娇  李菲  殷长秦 《环境科学》2019,40(4):1634-1644
通过对广州番禺大气成分站(GPACS)的光化学相关污染物(O3、PAN、VOCs、NO2、NO)以及气象要素进行观测,分析2010~2016年期间发生在广州地区一次典型光化学污染过程.结果表明,该光化学污染过程期间,O3和PAN总体体积分数比较高,最大O3小时体积分数为140.6×10-9,而最大PAN小时体积分数为4.7×10-9.NO整体体积分数较低,对O3的化学滴定和PAN的去除影响较小.NO2整体体积分数较高、辐射较强和风速较低则有利于O3和PAN的形成和积累.PAN和O3具有一定的线性关系(R2=0.55),而形成PAN和O3前体物VOCs物种不完全相同影响着它们的线性关系,在生成PAN的VOCs物种中,乙烯、丙烷、异戊二烯和甲苯所占的比例较大,而对臭氧生成潜势较大的物种有异戊二烯、1,3,5-三甲苯、丙烯、间,对-二甲苯以及甲苯.对PA自由基体积分数进行估算,发现它的日均值体积分数在0.11×10-12~0.16×10-12范围变化,远高于其它地区,表明此次发生的光化学反应较为强烈.  相似文献   

4.
Gaseous peroxides play important roles in atmospheric chemistry. To understand the pathways of the formation and removal of peroxides, atmospheric peroxide concentrations and their controlling factors were measured from 7:00 to 20:00 in September, October, and November 2013 at a heavily trafficked residential site in Beijing, China, with average concentrations of hydrogen peroxide (H2O2) and methyl hydroperoxide (MHP) at 0.55 ppb and 0.063 ppb, respectively. H2O2 concentrations were higher in the afternoon and lower in the morning and evening, while MHP concentrations did not exhibit a regular diurnal pattern. Both H2O2 and MHP concentrations increased at dusk in most cases. Both peroxides displayed monthly variations with higher concentrations in September. These results suggested that photochemical activity was the main controlling factor on variations of H2O2 concentrations during the measurement period. Increasing concentrations of volatile organic compounds emitted by motor vehicles were important contributors to H2O2 and MHP enrichment. High levels of H2O2 and MHP concentrations which occurred during the measurement period probably resulted from the transport of a polluted air mass with high water vapor content passing over the Bohai Bay, China.  相似文献   

5.
Rainwater samples were collected in Los Angeles, during 1985–1991 to determine concentration levels, sources and deposition rates of atmospheric H2O2, aldehydes and organic acids, in addition to major cations, anions and pH. Volume-weighted mean concentrations of H2O2, aldehydes (formaldehyde + acetaldehyde + glyoxal + methylglyoxal) and organic acids (formic acid + acetic acid) in rain collected at Westwood were 4.4., 3.9 and 16.5 μM, respectively, during the 6-year study period. Monocarboxylic organic acids were estimated to account for 27% (2–80%) of total free acidity (as on overall average) in rain collected at Westwood, whereas sulfuric acid and nitric acid accounted for 39% and 34% of the total acidity, respectively. Concentrations of aldehydes were strongly dependent on precipitation volume and decreased with increasing precipitation volume, whereas H2O2 and organic acids were only weakly dependent on precipitation volume. These results indicate that concentrations of aldehydes in rain are mainly controlled by dilution, whereas H2O2 and organic acid concentrations are controlled by other factors, such as decomposition of H2O2 by reacting with S(IV) and continuous aqueous formation/decomposition of organic acids by reactions involving aldehydes, dissolved OH radicals and H2O2. Principal component analyses indicate that aldehydes in rainwater mainly originate from gases and aerosols derived from anthropogenic sources, whereas the sources of H2O2 and organic acids in rain do not correlate with anthropogenic sources or marine and continental sources. There is good agreement between reported gas-phase concentrations of H2O2, aldehydes and organic acids in Los Angeles and calculated equilibrium concentrations of these chemical species from their rainwater concentrations and Henry's law constants. Temporal variations of concentrations of chemical species indicate that H2O2, aldehydes and organic acids were highest in the early afternoon. Summer rains contained the highest concentration of these chemical species, suggesting the photochemical activities during rain storms significantly affect their concentration levels. Estimation of annual rate of wet and dry depositions of H2O2, aldehydes and organic acids for the period studied, indicates that 84% of H2O2, 97% of aldehydes and 94% of organic acids, respectively, are annually scavenged from the atmosphere, by dry deposition, which is the dominant process for removal of these atmospheric pollutants in Los Angeles.  相似文献   

6.
对流层臭氧(O3)主要由氮氧化物(NOx)和挥发性有机物(VOCs)经过一系列光化学反应生成,反应过程呈现复杂的非线性关系.为深入了解O3的光化学特征及生成机制,利用2018年夏季大气O3与VOCs的观测数据,结合大气零维框架模拟模型F0AM-MCM,研究O3超标日和非O3超标日的O3光化学特征之间的差异性.观测结果表明,O3超标日期间φ(O3)和φ(TVOCs)的平均值分别为47.8×10-9和49.0×10-9,为非O3超标日期间O3(26×10-9)和TVOCs(30×10-9)体积分数的1.8倍和1.6倍.使用F0AM模型,借助EKMA曲线和RIR分析等识别O3敏感性,发现南京市O3超标日和非O3超标日O3的形成均主要受VOCs和NOx的协同控制.F0AM-MCM模拟结果表明,在O3超标日,·OH和HO2的日平均混合比分别是非O3超标日的1.3倍和1.8倍,表明O3超标日期间具有更强的大气氧化能力,且·OH和HO2的形成和损失速率也有明显的增加,表明自由基循环的增强.此外,O3超标日的O3生成速率明显高于非O3超标日,从而导致了O3超标日的O3净生成速率明显高于非O3超标日.以上发现提高了对南京夏季O3超标日大气O3光化学特征的认识.  相似文献   

7.
采用在线仪器监测分析2017年夏季天津气象铁塔220 m观测平台大气中过氧乙酰硝酸酯(PAN)和O_3的体积分数,并结合气象观测资料和后向轨迹分析PAN和O_3的输送特征.观测期间PAN和O_3体积分数平均值分别为(0.73±0.56)×10~(-9)和(53±25)×10~(-9),最大小时体积分数分别为3.49×10~(-9)和137×10~(-9),PAN和O_3体积分数具有相似的日变化特征,白昼PAN和O_3浓度高于夜间,且PAN和O_3浓度相关系数(R2=0.52)显著高于夜间(R2=0.21).观测期间偏南风下PAN和O_3浓度最高,偏东风下最低,风玫瑰图和后向轨迹聚类分析都表明,来源于西南方向的气流轨迹对应的污染物浓度最高,途经渤海和河北、辽宁沿海地区的偏东气流对应的PAN和O_3体积分数最低,边界层内输送对PAN和O_3的体积分数分布起到了重要作用.  相似文献   

8.
Atmospheric peroxyacetyl nitrate(PAN), peroxypropionyl nitrate(PPN), and carbon tetrachloride(CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring(October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer(March to August), ranging from 1.37–3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values(below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September(1.14 ppbV). The monthly variation of CCl4was tightly related to the variation of temperature, exhibiting a minimum in winter(69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon(ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn(R = 0.91), spring(R = 0.94), and summer(R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes( O3 / PAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3consumption by NO titration and less thermal decompositin of PAN.  相似文献   

9.
北京市大气光化学氧化剂污染研究   总被引:24,自引:3,他引:21  
根据在北京市开展的光化学氧化剂系列研究,讨论北京市主要光化学氧化剂O3,H2O2和有机过氧化物的污染浓度水平及其污染特征,探讨光化学氧化剂的形成机制及其主要影响因素。结果表明,北京市存在严重的光化学氧化剂污染,中关村大气臭氧(03)最大浓度不仅逐年递增,而O3最大值的出现时间也提前,说明大气光化学活性逐年增强。光化学烟雾的重要产物过氧化氢(H2O2)和甲基过氧化氢(MHP)的浓度水平较高,最大浓度分别为3.69和3.26ug/m3。日益严重的大气NOx污染为光化学氧化剂的生成提供了充足的前体物,北京市的大气污染己逐渐转为机动车尾气污染型,控制北京市光化学氧化剂污染的有效途径是降低NOx排放。   相似文献   

10.
Indoor and outdoor concentrations of the air pollutants ozone, NO2, SO2, H2S, total reduced sulfur (TRS), peroxyacetyl nitrate (PAN), methyl chloroform and tetrachloroethylene, have been measured at three southern California museums. Indoor maxima were 175 ppb for NO2, 77 ppb for O3, 0.7 ppb for PAN, 1.2 ppb for C2Cl4, >6.3 ppb for CH3CCl3, 2.5 ppb for SO2, 1.4 ppb for TRS, and 46 ppt for H2S. Indoor levels and indoor/outdoor (I/O) ratios for the chlorinated hydrocarbons pointed out to indoor sources. Outdoor and indoor levels of SO2 and TRS were low at all three museums, but I/O ratios for SO2 were high and averaged 0.89. H2S concentrations were low, 16–46 ppt at one museum and less than 6 ppt at the other two museums. I/O ratios for the air pollutants with outdoor sources (ozone, PAN and NO2) showed substantial variations, from low values of 0.02–0.33 at locations without influx of outdoor air to high values of 0.85–0.88 at locations experiencing high influx of outdoor air. Of the 10 institutions we have surveyed in southern California to date, eight exhibit high I/O ratios, e.g. 0.60–1.00 for PAN. Of the four museums surveyed that were equipped with HVAC and chemical filtration, only two yielded the expected low I/O ratios.  相似文献   

11.
A new zonally averaged two-dimensional chemical and transport model of the lower atmosphere has been used to study the budgets of photochemical oxidants on a global scale in the troposphere. The sensitivities of these budgets to controls on the emissions of NOx, CO and hydrocarbons from a variety of sources have also been considered. The species studied include O3, PAN, H2O2 and organic peroxides, as well as the global budget of the hydroxyl radical. The results show the relative impacts of emissions from natural and from man-made sources. Overall, some 75% of the turnover of tropospheric ozone results from in situ chemical production, with only 25% having its origins in the stratosphere. The respective fractions for chemical loss and dry deposition are similar. Of the ozone formed in situ, approximately one-third is formed from natural emissions, and two-thirds from man-made emissions. Over half of this man-made contribution is due to industrial society, with much of the rest being caused by biomass burning and methane emitted from paddy fields. Although reducing emissions of NOx is the most effective way of controlling tropospheric O3, this also increases the inventories of peroxides and the rate of increase in the concentration of methane, due to a reduction in the inventory of the OH radical. It is, therefore, necessary to control the emissions of a wide range of species in order to reduce the budget of all photochemical oxidants without adversely perturbing the budget of CH4.  相似文献   

12.
Previous measurements of peroxyacetyl nitrate(PAN) in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site(CMA) in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10 9mol/mol(0.23 × 10 9–3.51 × 10 9mol/mol) and was well correlated with that of NO2but not O3, indicating that the variations of the winter concentrations of PAN and O3in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3ratio smaller than 0.031, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl(PA) radical was estimated to be in the range of 0.0014 × 10 12–0.0042 × 10 12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN's variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.  相似文献   

13.
Concentrations of atmospheric H2O2 were measured in air, rain, cloud and dew samples in forested areas of the San Bernardino Mountains, southern California, from spring through fall of 1987–1990 O3 measurements in air were also conducted for comparison. Typical ranges of H2O2 concentrations measured were 1–3 ppb in air, 10–90 μM in rain and cloud water, and < μM in dew. The results show that gas-phase H2O2 concentrations were slightly higher at nighttime than at daytime or nearly constant throughout a 24-hr period, whereas O3 concentrations were highest during the afternoon, when polluted air masses from Los Angeles carried by daily sea breezes reached the mountain region. Afternoon concentrations of gaseous H2O2 and O3 in the mountain region were compared with those measured in Los Angeles urban sites to elucidate the regional variation of these oxidants. The results show that ambient concentrations of H2O2 and O3 were about 50–100% higher at the mountains sites than at the Los Angeles sites.  相似文献   

14.
An O3 episode observed at Dorset, a rural site in central Ontario, during a stagnant high pressure period of the intensive Eulerian Model Evaluation Field Study (EMEFS), in the summer of 1988, is simulated using a photochemical box model with a two-layer treatment. In the model analysis, natural hydrocarbon chemistry is simulated based on an isoprene-only scenario. Sensitivity tests indicate that local isoprene emissions are an important contributor to local O3 production, relative to anthropogenic hydrocarbons (AHCs), during the event.The model calculated isoprene contribution to the local O3 production, defined as the ratio of the O3 amount formed in the absence of AHCs to that in the presence of AHCs, is characterized by a strong NOx dependence. A minimum value (∼50%) of the contribution was found at a NOx level of ∼ 6 ppbv for the representative hydrocarbon composition during the episode. At this NOx level, O3 production was strongly influenced by the presence of AHCs. At significantly higher or lower NOx levels, isoprene is more important than AHCs in the local O3 production.  相似文献   

15.
泰安市大气臭氧污染特征及敏感性分析   总被引:1,自引:0,他引:1  
李凯  刘敏  梅如波 《环境科学》2020,41(8):3539-3546
2018年5~7月对泰安市城区站点的臭氧及前体物进行在线监测,并基于特征比值法和光化学模型分析了臭氧及前体物的污染特征及臭氧生成对前体物的敏感性.结果表明,观测期间泰安市正遭受较为严重的臭氧(O3)污染,臭氧浓度的日变化呈典型的单峰型变化,15:00左右出现最高值,氮氧化物(NOx)和VOCs的日变化趋势整体呈现夜间高白天低的变化特征.由O3生成效率(OPE)、VOCs/NOx和H2O2/NOz特征比值法及基于EKMA曲线的方法均得出观测期间泰安市大气O3光化学生成偏向于NOx敏感区及过渡区,削减NOx和VOCs均对O3生成具有控制作用.同时基于EKMA曲线的方法还得出在O3前体物浓度减排时按照丙烯等效浓度(PE)与NOx浓度比值为8∶3进行VOCs(PE)和NOx削减可以达到O  相似文献   

16.
Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.  相似文献   

17.
The long-range transport of air pollutants (LRTAP) over Europe is studied by a mathematical model based on a system of partial differential equations (PDEs). The number of PDEs is equal to the number of species studied and the model contains 35 species at present. Among the species are NO, NO2, NO3, HNO3, NH3, NH4+, O3, PAN, SO2, SO42− and may hydrocarbons. Most of the 70 chemical reactions involved in the model are nonlinear (including here many photochemical reactions).The model requires large sets of input data. Emissions of SO2, NOx, NH3 and both natural and anthropogenic volatile organic compounds (VOC) are needed in the model. The meteorological data consist of fields of wind velocities, precipitation, surface temperatures, temperatures of the boundary layer, relative humidities and cloud cover, which are read in the beginning of every 6-h interval. Both daytime and nighttime mixing heights are used in the model.Many of the species in the model vary on a diurnal basis. An investigation of the main mechanisms that determine the diurnal variation of the ozone concentrations is performed. One of the important conditions that is necessary if one wants to represent correctly the diurnal variations of the concentrations is to have access to meteorological data that vary diurnally. This is especially true for the temperature and the mixing height.The use of modern numerical algorithms (which are combined with vectorization of the most time-consuming numerical procedures) allows one to perform long-term runs with the model on several high-speed computers. Results obtained in runs with meteorological data for July 1985 and August–October 1989 are discussed. The computed concentrations and depositions are compared with measurements taken at stations located in different European countries. The agreement between calculated concentrations and measurements is reasonably good.Results obtained with several scenarios, in which the NOx emission and/or the anthropogenic VOC emissions are varied, are presented. Several main conclusions are drawn by studying the results obtained during the comparisons. Some plans for future development of the models are discussed.  相似文献   

18.
张薛  赵璇 《环境科学学报》2015,35(3):750-755
表面活性剂是一类特殊的有机污染物,在去污、洗衣、印染等废水中广泛存在.本文以某电厂实用的5种去污剂为研究对象,考察了UV/H2O2对5种去污剂的矿化能力,研究了H2O2和去污剂初始浓度、初始p H值、去污剂种类、辐照时间等因素对氧化效果的影响.结果表明,5种去污剂在254 nm处均无较强吸收,单独UV辐照对其降解效果不明显.当去污剂初始DOC浓度为50 mg·L-1,H2O2最佳投加量为1 m L·L-1,反应时间为90 min时,对5种去污剂的矿化率(即DOC去除率)在53%~87%,矿化率随去污剂种类的不同而不同.对去污剂的矿化率随着UV辐照时间的延长而增大,去除率曲线符合一级反应动力学方程.废水初始p H值对氧化效果的影响不显著,H2O2/DOC比值对氧化效果有显著影响.研究表明,UV/H2O2技术能高效矿化水中的去污剂,H2O2/DOC比值和UV辐照时间是影响氧化效率的关键因素.  相似文献   

19.
为进一步优化柴油机燃烧过程,减少燃烧污染物排放.围绕EGR(exhaust gas recirculation,废气再循环技术)废气组分和废气温度等系统参数对柴油机燃烧特征的影响机制,采用试验与模拟相结合方法,分别研究了通入废气、N2、CO2时以及不同EGR废气温度时对柴油机燃烧过程的影响,阐明了燃烧关键中间产物的生成规律.结果表明,①通入CO2时,柴油机的缸内最大爆发压力和放热率峰值最低,滞燃期最长,燃烧持续期最短,·OH、H2O2、CH2O·和CO等关键中间组分的生成规律与通入N2时相反.②通入N2时,柴油机的缸内最大爆发压力和放热率峰值最高,滞燃期最短,燃烧持续期最长并;并且通入N2时,·OH的峰值最高,形成时刻最早,H2O2、CH2O·以及CO的峰值均有所降低且形成时刻提前.③随着废气温度增加,缸内最大爆发压力降低,放热率曲线由单峰向双峰分布发展,放热率峰值有较大幅度的降低,滞燃期缩短,燃烧持续延长,缸内·OH、H2O2、CH2O·以及CO的峰值均有所降低,并且生成的区域范围变窄.④废气成分中,CO2对燃烧过程和关键中间产物的影响最大,是阻滞燃烧反应的主要气体成分,通过控制EGR废气成分和温度可以有效改善柴油机燃烧过程,拓宽EGR技术的工况使用范围.研究显示,EGR废气成分对燃烧中间产物的自由基衍化历程影响较大,有必要进一步开展EGR废气成分预处理研究,精确控制EGR废气温度,有助于改善燃烧过程,控制排放污染物中间产物的生成历程和排放量.   相似文献   

20.
济南大气臭氧浓度变化规律   总被引:12,自引:3,他引:12  
殷永泉  单文坡  纪霞  由丽娜  苏元成 《环境科学》2006,27(11):2299-2302
利用近2a济南市区近地面大气O3浓度的观测数据,分析了O3浓度的分布特征及时间变化规律.结果表明,济南市区O3浓度以1a为周期呈明显的波动变化特征,城市光化学污染较重;1d当中O3浓度呈明显的单峰型变化,一般在午后达到最高值,而日出时分出现最低值;春季和夏季O3浓度高于秋季和冬季,而夏季和秋季O3浓度的日内变化幅度明显高于春季和冬季;受人们活动规律的影响,周末O3浓度的日内变化规律与平日有所不同.  相似文献   

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