许昌市臭氧污染趋势及时空分布特征研究

为研究许昌市的臭氧(O3)污染情况及时空分布特征,对2014年-2016年许昌市3个国家环境空气监测点位的监测数据进行了统计分析.结果表明:2014年-2016年,许昌市O3污染状况整体呈加重趋势,2016年污染最为严重;O3浓度和超标天数均具有明显的季节变化特征,春末和夏季的O3污染最为严重;不同季节的O3、NO2、NO和NOx浓度日变化也不尽相同,同时O3具有明显的日变化特征,呈单峰型分布,峰值出现在14:00~15:00;并且O3与NO2具有较好的相关性.     

Surface ozone in rural,urban and alpine regions of switzerland

The study shows the variation of surface ozone concentrations for six selected sites between 410 and 3569 m elevation. The annual mean values in 1987 for these sites ranged from 10 to 50 ppb. Mean values of ozone as well as frequency of peak values are clearly dependent on the elevation of the site. Apart from elevation the influences of the specific location and exposure to pollutants such as NO and NO₂ are considered. The ratio of the daily means of NO and NO₂ is very well suited to indicate local sources. Mean diurnal concentration variations of nitric oxide and ozone on a slope show a significant influence of topography.     

Heterogeneous chemistry on polar stratospheric clouds

Polar stratospheric clouds play a crucial role in the depletion of stratospheric ozone over Antarctica in the spring months. The cloud particles promote the conversion of the inert chlorine reservoirs HCl and ClONO₂ to Cl₂, which is photolytically active. Furthermore, the clouds lead to the removal of nitric acid and nitrogen oxides from the gas phase, facilitating the destruction of ozone by catalytic cycles involving chlorine free radicals.     

Characteristics of urban ozone level in Hong Kong

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Relationship of non-methane hydrocarbons and NOx to ozone formation in the atmosphere of Bahrain

The hourly air quality monitoring data for hydrocarbons, NO_x, and ozone were analyzed from two sites; one north of the industrial areas in Sitra and the other one located south on the east coast. The background levels of non-methane hydrocarbons at both sites were in excess of the U.S. federal ambient air quality standard of 0.24 ppm most of the time. The U.S. ozone air quality hourly standard of 0.12 ppm. however, was exceeded twice only at Sitra during high ambient NO _x concentrations greater than 0.15 ppm and high non-methane hydrocarbon levels of 10 ppm. The suitability of introducing the U.S. standard for non-methane hydrocarbons to the region is discussed.     

海南省背景区域臭氧及其前体物污染特征

基于2019年五指山背景点、海口市和三亚市的环境空气自动监测数据和气象观测资料,分析了海南省背景区域和重点城市O₃及其前体物NO₂污染特征;结合挥发性有机物（VOCs）在线监测数据,分析了五指山背景点VOCs的时间变化规律、O₃浓度高值月份O₃及其前体物VOCs和NO_x的污染特征以及VOCs的臭氧生成潜势（OFP）.结果表明,O₃是影响五指山背景点空气质量的关键污染物,五指山背景点O₃日最大8 h浓度平均值与海口市和三亚市显著相关.背景点NO₂月均浓度水平显著低于城市点,然而背景点和城市点O₃月均浓度水平和变化趋势高度一致.背景点O₃变化与风向密切相关,春夏季偏南风频率较高,O₃浓度相对较低;秋冬季以东北风为主,易受内陆污染输送影响,O₃浓度较高.五指山背景点春夏季VOCs体积分数低于秋冬季,但对应的OFP高于秋冬季;其中异戊二烯夏季体积分数显著高于秋冬季,且其夏季体积分数占总挥发性有机物的比例最高,对应的OFP贡献率可达70%以上,O₃则表现出秋冬季显著高于夏季的特征.11月O₃高浓度时段乙炔和芳香烃的体积分数较清洁日出现较大上升,同时其对应的OFP显著上升.VOCs优势物种和OFP主要贡献物种的分析结果表明,O₃高浓度时段机动车尾气和油气挥发排放源对五指山背景点VOCs的化学组成和OFP有重要贡献.     

2014年6月南京大气复合污染观测

二次无机盐是PM_2.5的重要组成部分,厘清污染过程中二次无机盐的演变过程和影响因素,是提高对污染过程认识的关键.以2014年6月南京地区两次污染事件为例,研究了污染过程中二次无机盐的演变过程和影响因素.结果表明,两次污染过程均表现出显著的大气复合污染特征;污染初期,臭氧浓度较高,大气氧化性强,气态硝酸具有较高的生成潜势,为细颗粒物中NO₃^-的快速生成创造前提条件,后期相对湿度（RH）升高对NO₃^-的生成起决定性作用;当RH大于多组分的共同潮解相对湿度（DRH^*）时,NH₄NO₃潮解平衡时NH₃和HNO₃的理论分压积显著降低,低于观测得到的分压积,有利于NO₃^-生成,同时,观测和理论的分压积差异能够很好地表征NO₃^-的浓度变化特征.     

夏季长三角地区臭氧非线性响应曲面模型的建立及应用

2013年8月上旬,长三角地区发生了一次大范围高浓度臭氧污染事件.本研究基于WRF-CMAQ空气质量模型系统,结合长三角地区大气污染物排放清单,构建了臭氧与其前体物之间的非线性响应曲面模型(Response surface modeling,RSM).基于RSM探讨了长三角地区O_3化学的敏感性特征,分析了上海市O_3的来源并预测不同情景下O_3的变化,提出O_3污染的最优控制方案.研究结果表明,长三角地区夏季O3主控因素区域差别较大,上海环科院、杭州卧龙桥、南京玄武湖等城区点位属于VOC控制型;徐州铜山、合肥肥西、丽水青田等郊区属于NOx控制型.O_3的敏感性特征在不同浓度水平下也呈现较大差异,随着O_3浓度水平的升高,各地区NOx敏感性均有所增加.从区域来源来看,远距离传输对平日上海O_3贡献较大,占50%以上;而在O_3污染日,本地及区域贡献为72.1%,而远距离传输贡献下降至27.9%.快速预测了110组减排情景,表明在本地及区域前体物均减排70%的情况下,2013年8月上海O_3浓度能完全达标.     

A captive-air irradiation study of the response of nitric acid and peroxyacetyl nitrate to ozone control strategies in Los Angeles

Outdoor smog chamber experiments were used to study the sensitivity of the yields of two important nitrogen-containing pollutants, nitric acid (HNO₃) and peroxyacetyl nitrate (PAN) to changes in nonmethane hydrocarbon (HC) and nitrogen oxide (NO_x) concentrations in Los Angeles. The experiments were conducted at two sites in the Los Angeles Basin using eight chambers filled with morning Los Angeles air on 33 days. At least one chamber was unchanged and served as a control, while the initial HC and/or NO_x concentrations were changed by 25–50% in up to seven chambers to simulate O₃ control strategies and to broaden the range of HC - NO_x conditions studied. Empirical models that predict the maximum yields of HNO₃ and PAN were used to determine the response of these pollutants to three possible ozone control strategies. All three strategies (reductions in HC, NO_x or both HC and NO_x) reduced PAN while only NO_x reductions decreased HNO₃. However, reducing NO_x increased the HC reductions required to attain lower O₃ levels. Thus, there is a conflict between the O₃ and HNO₃ control strategies.     

Effects of building aspect ratio, diurnal heating scenario, and wind speed on reactive pollutant dispersion in urban street canyons

A photochemistry coupled computational fluid dynamics (CFD) based numerical model has been developed to model the reactive pollutant dispersion within urban street canyons, particularly integrating the interrelationship among diurnal heating scenario (solar radiation affections in nighttime, daytime, and sun-rise/set), wind speed, building aspect ratio (building-height-to-street-width), and dispersion of reactive gases, specifically nitric oxide (NO), nitrogen dioxide (NO₂) and ozone (O₃) such that a higher standard of air quality in metropolitan cities can be achieved. Validation has been done with both experimental and numerical results on flow and temperature fields in a street canyon with bottom heating, which justifies the accuracy of the current model. The model was applied to idealized street canyons of different aspect ratios from 0.5 to 8 with two different ambient wind speeds under different diurnal heating scenarios to estimate the influences of different aforementioned parameters on the chemical evolution of NO, NO₂ and O₃. Detailed analyses of vertical profiles of pollutant concentrations showed that different diurnal heating scenarios could substantially affect the reactive gases exchange between the street canyon and air aloft, followed by respective dispersion and reaction. Higher building aspect ratio and stronger ambient wind speed were revealed to be, in general, responsible for enhanced entrainment of O₃ concentrations into the street canyons along windward walls under all diurnal heating scenarios. Comparatively, particular attention can be paid on the windward wall heating and nighttime uniform surface heating scenarios.     

Cost effective environmental control technology for utilities

On September 24, 1998, new regulations announced by the US EPA require 22 eastern states plus the District of Columbia to develop state implementation plans to reduce ground-level ozone through the reduction of nitrogen oxide (NOx) emissions (Cooper, 1998). This plan calls for a 28% NOx cut in the summer time (1.2 million tons) by 2007. This calls for utilities to develop new, efficient, and robust post-combustion NOx control technologies. A new environmental control technology called low temperature oxidation (LTO) system, which can reduce NOx emissions below measurable levels (i.e. 2 ppm using process analyzers) at low temperature (125-325 °F), was awarded the best available control technology and the lowest available emission reduction technology by the US EPA in April 1998. Ozone is employed to oxidize nitric oxide (NO) to dinitrogen pentoxide (N₂O₅) at a low temperature in an oxidizer, which is then easily absorbed by water in a scrubber. Bench scale and pilot plant tests have shown that the LTO process can almost completely remove the NOx emissions (i.e. NOx emissions are below levels measurable using process analyzers). This proved that the LTO system is an attractive process to meet the stricter NOx regulations. There are multiple benefits of the LTO system besides removal of NOx emissions, includes reduction of SOx and CO emissions, and no secondary air emissions (NH₃, N₂O). In order to obtain minimum NOx emissions, extra ozone needs to be supplied. The cost of the process also increases nonlinearly as emissions decrease. This poses a challenging multiobjective optimization problem where emissions like NOx and SOx need to be minimized, while minimizing the system cost as well as extra ozone. This problem is addressed using a new and efficient multiobjective optimization framework. This framework will provide designs that are cost effective as well as environmentally friendly.     

Photochemical model calculations over Europe for two extended summer periods: 1985 and 1989. Model results and comparison with observations

Ozone concentrations over Europe have been calculated with the EMEP MSC-W ozone model for two extended summer periods: April–September 1985 and April–October 1989. The predicted monthly variations in both mean and elevated ozone levels are illustrated. The model is shown to compare satisfactorily with ozone data across nearly all the months studied, particularly in 1989. Modelled PAN and total airborne nitrate concentrations are also shown to compare favourably with the measurements of a Nordic measurement campaign in autumn 1989, although there is an unresolved discrepancy between the modelled and observed NO₂ at these sites. In addition, the model has now been used to estimate the effects of NO_x and volatile organic compound emission control on both mean and elevated ozone levels for 6 months in 1989.     

深圳市2022年春季新冠疫情管控期间空气质量分析

短期减排是我国城市应对大气污染事件的重要应急管控手段,但短期减排的效益尚未得到完善分析.2022年3月14～20日,广东省深圳市为抑制新冠疫情传播实施了全市管控,为评估短期减排对华南城市春季空气质量的影响提供独特机会.结合深圳市高精度环境空气质量监测与气象观测等多源数据,分析了深圳市管控期间前后的空气质量变化.此次管控前和管控期中均有部分日期天气形势静稳,局地污染水平主要反映本地排放,有利于分析本地减排的影响.观测与WRF-GC区域化学模拟都表明,与珠三角周边城市相比,深圳市管控期间由于市内交通源排放显著减少,深圳市二氧化氮(NO₂)浓度降低(-26±9.5)%,可吸入颗粒物(PM₁₀)浓度降低(-28±6.4)%,细颗粒物(PM_2.5)浓度降低(-20±8.2)%,但臭氧(O₃)浓度无显著变化[(-1.0±6.5)%].TROPOMI卫星观测的甲醛和二氧化氮柱浓度数据对比表明,2022年春季珠三角臭氧光化学主要受挥发性有机物(VOCs)浓度控制,对氮氧化物浓度降低不敏感,反而可能因氮氧化物对臭氧滴...     

一个沿海城市大气臭氧的本地生成过程及其对前体物的敏感性

在威海市两个采样点用苏码罐采集了全空气样品,利用三级冷阱预浓缩-GC/MS方法离线测定了空气样品中109种大气挥发性有机物(VOCs).使用基于观测的MCM机理大气化学模式(OBM-MCM)分析了大气臭氧生成对VOCs组分的敏感性及本地生成过程.结果表明:观测期间两个采样点的总挥发性有机物(TVOCs)平均浓度分别为27.84×10~(-9)和17.85×10~(-9),对TVOCs贡献最大的均是烷烃.模拟分析表明,大气臭氧生成与前体物的控制关系存在空间差异性,在一个观测点受VOCs控制,而在另一个观测点受NO_x和VOCs共同控制;模拟结果还表明,臭氧生成对活性烃类最为敏感,但是,含氧有机物、卤代烃和高碳烷烃对臭氧生成的影响和贡献也不可忽视;此外,计算了日平均臭氧净生成速率P(O_3)_(net),分别为6.41×10~(-9) h~(-1)和3.22×10~(-9) h~(-1),臭氧的本地生成过程扮演重要角色.     

济南大气臭氧浓度变化规律

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.     

高能电子沉降对北半球冬季中高层大气活性氮和臭氧影响的数值模拟

高纬度地区平流层臭氧浓度对极地地表生物地球化学过程影响巨大,近年来高能电子沉降对大气臭氧和活性氮的影响成为新的关注点。本工作基于化学-气候耦合模式SOCOL3.0,参考第六次耦合模式比较计划（CMIP6）推荐的低能量电子（LEE）和中能量电子（MEE）的参数化方案构建了SOCOL-EPP-ECNU化学-气候模式,利用该模式对高能电子沉降对中高层大气活性氮（NO_x）和臭氧的影响进行了敏感性试验和评估。结果表明,中高层大气对于LEE效应产生的NO_x通量的上边界条件设定敏感度很高,该设定对模式模拟效果有决定性意义。加入LEE和MEE通量后,模式对北半球冬季平流层中下层NO_x浓度的模拟精度得到提高,同时也使北半球冬季平流层中下层气温的模拟得到改善。模拟结果指示,加入LEE和MEE,进一步完善对高能粒子沉降的模式描述,有助于提高模式对大气化学成分及气候要素模拟的准确度。     

上海市光化学污染期间挥发性有机物的组成特征及其对臭氧生成的影响研究

光化学污染导致的高浓度臭氧(O3)是上海面临的重要大气污染问题.本研究分别选取了市区(徐汇)、城郊(青浦)和郊区(南汇)3个典型地区在夏季光化学污染易发季节开展了O3及其前体物挥发性有机物(VOCs)和氮氧化物(NOx)的观测,结合光化学箱模型研究探讨了O3生成的主控污染物.研究表明,不同地区O3污染呈现较强的同步性,日最大浓度也比较接近;但南汇郊区由于受机动车排放影响较小,NOx浓度显著低于其他两个地区,导致该地区O3浓度日变化曲线相对平缓,夜间O3浓度也维持在较高水平.大气VOCs浓度较高时,往往伴随高浓度的O3;3个地区VOCs浓度和组成差异明显,就VOCs浓度而言,徐汇青浦南汇;浓度贡献最主要的物种为甲苯、C2~C3的烷烃和烯烃、丙酮以及辛烷;而C7~C10芳香烃、C3~C4的烯烃、异戊二烯以及乙醛是上海大气臭氧生成潜势贡献最大的VOCs类物质.3个地区O3的生成主要受人为排放的二甲苯类和C3~C4烯烃类物质控制;对于徐汇,只控制NOx会导致O3浓度升高,而南汇郊区O3的生成对NOx排放不敏感.     

河北与京津地区非采暖期大气中的PAHs污染特征

对河北与京津地区42个样点非采暖期大气中多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)的研究表明,该区域大气中的PAHs浓度水平较高.2～3环PAHs主要分布在气相当中,颗粒相(大气可吸入颗粒物,PM10)中PAHs以4～6环为主.PAHs的高浓度样点在石家庄、唐山和邯郸地区分布最为集中.县城样点与城市样点的PM10和PAHs污染水平相近.临近区域广泛存在的大气污染很可能对北京市的大气环境造成影响.     

Formic acid and acetic acid in the western Sierra Nevada,California

This paper reports the results of measurements of formic and acetic acid at four sites located along the western slope of the Sierra Nevada and compares the results with those of earlier studies. Formic acid concentrations ranged from approximately 1 to 40 ppb; those of acetic acid ranged from approximately 0.5 to 13 ppb. Mean formic acid concentrations were 18 ppb at Tehachapi, located at the southern extremity of the range, and between 12 and 13 ppb at the three other sites. Mean acetic acid concentrations ranged from 3.9 ppb at Blodgett Experimental Forest, located at the northern extremity, to 8.0 ppb at Yosemite. Comparison with previous studies indicates that carboxylic acid levels measured in the Sierra Nevada are higher than those measured in past studies, and in many cases average concentrations of both formic and acetic acids observed during this study were greater than the previously reported maxima. Comparisons were also made to nitric acid concentrations measured at Yosemite and Giant Forest from October 1986 to September 1987. At Yosemite, annual nitric acid concentrations averaged 0.20 ppb during the day, and 0.06 ppb at night; and at Giant Forest, nitric acid averaged 0.17 ppb during the day, and 0.05 ppb at night. Thus, the high formic and acetic acid concentrations observed in this study suggest that carboxylic acid are major contributors to the overall flux of ambient acid deposition in the western Sierra Nevada.     

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Br?nsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Br?nsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.