Aerosol effects on ozone concentrations in Beijing: A model sensitivity study

Most previous O₃ simulations were based only on gaseous phase photochemistry. However, some aerosol-related processes, namely, heterogeneous reactions occurring on the aerosol surface and photolysis rate alternated by aerosol radiative influence, may affect O₃ photochemistry under high aerosol loads. A three-dimensional air quality model, Models-3/Community Multi-scale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution, was employed to simulate the effects of the above-mentioned processes on O₃ formation under typical high O₃ episodes in Beijing during summer. Five heterogeneous reactions, i.e., NO₂, NO₃, N₂O₅, HO₂, and O₃, were individually investigated to elucidate their effects on O₃ formation. The results showed that the heterogeneous reactions significantly affected O₃ formation in the urban plume. NO₂ heterogeneous reaction increased O₃ to 90 ppb, while HO₂ heterogeneous reaction decreased O₃ to 33 ppb. In addition, O₃ heterogeneous loss decreased O₃ to 31 ppb. The effects of NO₂, NO₃, and N₂O₅ heterogeneous reactions showed opposite O₃ concentration changes between the urban and extra-urban areas because of the response of the reactions to the two types of O₃ formation regimes. When the aerosol radiative influence was included, the photolysis rate decreased and O₃ decreased significantly to 73 ppb O₃. The two aerosol-related processes should be considered in the study of O₃ formation because high aerosol concentration is a ubiquitous phenomenon that affects the urban- and regional air quality in China.     

Measurement of hydrogen peroxide and organic hydroperoxide concentrations during autumn in Beijing, China

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.     

Ozone concentrations at a remote mountain site and at two regional locations in southwestern Alberta

Ozone concentrations at a remote site in the Rocky Mountains of southwestern Alberta averaged 43.4 ppb over a 2 year period and the Canadian air quality objective of an 80 ppb hourly average was exceeded 1.5% of the time. The diurnal variation in O₃ concentrations was small, 2.9 ppb, indicative of a remote location, above the nocturnal inversion and not greatly influenced by local emissions. During the period when O₃ concentrations were highest, winds were generally from the southwest, suggestive of the long range transport of anthropogenic pollutants from distant sources rather than the generation of O₃ from local emissions. In contrast, hourly O₃ concentrations at two regional air quality monitoring sites showed an average diurnal variation of 14 ppb. Only two hourly averages exceeded 80 ppb during the 2 years, and the mean O₃ concentration was 26 ppb. When these regional sites were within the urban plume from Calgary, the O₃ concentrations were depressed to a mean of 18 ppb. Ozone concentrations in downtown Calgary averaged 13 ppb. Under Alberta climatological and meteorological conditions, hourly O₃ objectives are most likely to be exceeded in remote areas, rather than in cities or in areas under the direct influence of urban emissions.     

Large-scale distribution of hydrogen peroxide from aircraft measurements during the TROPOZ II experiment

Aircraft measurements of hydrogen peroxide (H₂O₂) were performed during the TROPOZ II meridional campaign. A specially designed automatic H₂O₂ analyser on board the airplane allowed us to obtain more than 43,000 H₂O₂ measurements. The data set covers a latitude range from 60°N to 60°S and altitudes up to 11 km. Concentration of H₂O₂ ranged from 0.42 ppb (percentile 5) to 6.31 ppb (percentile 95) and exhibited a variability factor of as much as 15. Hydrogen peroxide concentration was typically low (<2 ppb) in the boundary layer of both hemispheres except for the inter-tropical belt, even in America, as well as Africa where the mean mixing ratio reached 5 ppb. In the northern uppermost troposphere a significant increase in H₂O₂ (>3 ppb) could be noticed. Some episodes of high hydrogen peroxide mixing ratio were encountered in the vicinity of cloud systems probably by exchange of H₂O₂ from the liquid phase to the gas phase.     

Sulfur dioxide,hydrogen sulfide,total reduced sulfur,chlorinated hydrocarbons and photochemical oxidants in southern California museums

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.     

2021年夏季新乡市城区臭氧超标日污染特征及敏感性

基于2021年6～8月新乡市市委党校站点观测的挥发性有机物(VOCs)、常规空气污染物和气象参数,采用基于观测的模型(OBM)对臭氧(O₃)超标日的O₃敏感性和前体物的管控策略进行了研究.结果发现,O₃超标日呈现高温、低湿和低压的气象特征.在臭氧超标日,O₃及其前体物的浓度均有上升.臭氧超标日的VOCs最高浓度组分为含氧挥发性有机物(OVOCs)和烷烃,臭氧生成潜势(OFP)和·OH反应性最大的VOCs组分为OVOCs.通过相对增量反应性(RIR)分析,新乡6月O₃超标日臭氧生成处于VOCs控制区,7月和8月处于VOCs和氮氧化物(NO_x)协同控制区,臭氧生成对烯烃和OVOCs最为敏感.6月各前体物的RIR值在一天中会发生变化,但始终保持为VOCs控制区;7月和8月在上午为VOCs控制区,中午为协同控制区,下午分别为协同控制区和NO_x控制区.通过模拟不同前体物削减情景,结果表明削减VOCs始终有利于管控臭氧,而削减NO_x     

乌海市夏季臭氧污染特征及基于过程分析的成因探究

乌海市地形复杂,周边工业园区分布密集,近年来夏季O₃污染问题突出,且污染特征与形成机制尚不明确,分析乌海市O₃变化特征,探究O₃污染形成机制对该区域大气污染防治具有重要意义.本文在分析乌海市2018年6~8月3次持续O₃污染过程特征的基础上,利用WRF-CMAQ模式系统进行模拟并根据过程分析输出结果对污染的成因进行了深入分析,探讨了区域输送和局地光化学反应对乌海市O₃的影响.结果表明,乌海市夏季O₃呈现"单峰"的日变化特征,近地面O₃与向下短波辐射和气温显著呈正相关,与相对湿度呈负相关;空间分布上,乌海市3个工业园区白天和夜间均为O₃低值区,乌海西南部宁夏石嘴山地区、乌海城区和西北部乌兰布和沙漠地区白天为O₃高值区;过程分析结果表明,输送和化学过程及其相对大小对乌海市O₃有决定性影响,6月和7月的污染过程中局地光化学反应和输送共同导致O₃显著升高,且化学过程的影响是输送的两倍左右,8月O₃的升高主要为输送作用的贡献;进一步对输送作用进行分解可知偏南和西北方向的输送对O₃的升高有较大贡献,结合前体物的排放,可能的传输来源为宁夏银川、石嘴山及巴彦淖尔等区域,因此,乌海市应在控制本地排放的基础上,加强区域联防联控,减少区域传输对O₃的影响.     

Seasonal,diurnal and nocturnal variations of carbonyl compounds in the semi-urban environment of Orléans,France

Atmospheric carbonyls were measured at a semi-urban site in Orléans, France, from October 2010to July2011. Formaldehyde, acetaldehyde and acetone were found to be the most abundant carbonyls, with average concentrations of 3.1, 1.0, 2.0 ppb, respectively in summer, 2.3, 0.7, 2.2 ppb, respectively in autumn, 2.2, 1.0, 2.1 ppb, respectively in spring,and 1.5, 0.7, 1.1 ppb, respectively in winter. Photo-oxidation of volatile organic compounds(VOCs) was found to make a remarkable contribution to atmospheric carbonyls in the semi-urban site based on the distinct seasonal and diurnal variations of the carbonyls, as well as the significantly positive correlations between the carbonyls and ozone. The significantly negative correlations between NO x and O_3 as well as the carbonyls and the positive correlations between wind speed and O_3 as well as the carbonyls implied that the carbonyls and O_3 at the semi-urban site were probably formed during air mass transport from neighboring cities.     

Observations of N2O5 and NO3 at a suburban environment in Yangtze river delta in China: Estimating heterogeneous N2O5 uptake coefficients

The nitrate radical (NO₃) and dinitrogen pentoxide (N₂O₅) play an important role in the nocturnal atmosphere chemistry. Observations of NO₃ radicals and N₂O₅ were performed in a semirural ground site at Tai'Zhou in polluted southern China using cavity ring down spectroscopy (CRDS) from 23 May to 15 June 2018. The observed NO₃ and N₂O₅ concentrations were relatively low, with 1 min average value of 4.4 ± 2.2 and 26.0 ± 35.7 pptV, respectively. The N₂O₅ uptake coefficient was determined to be from 0.027 to 0.107 based on steady state lifetime method. Fast N₂O₅ hydrolysis was the largest contributor to the loss of NO₃ and contributed to substantial nitrate formation, with an average value of 14.83 ± 6.01 µg/m³. Further analysis shows that the N₂O₅ heterogeneous reactions dominated the nocturnal NO_x loss and the nocturnal NO_x loss rate is 0.14 ± 0.02 over this region.     

Large variability in ambient ozone sensitivity across 19 ethylenediurea-treated Chinese cultivars of soybean is driven by total ascorbate

The sensitivity of Chinese soybean cultivars to ambient ozone(O3) in the field is unknown,although soybean is a major staple food in China. Using ethylenediurea(EDU) as an O3 protectant, we tested the gas exchange, pigments, antioxidants and biomass of 19 cultivars exposed to 28 ppm·hr AOT40(accumulated O3 over an hourly concentration threshold of40 ppb) over the growing season at a field site in China. By comparing the average biomass with and without EDU, we estimated the cultivar-specific sensitivity to O3 and ranked the cultivars from very tolerant( 10% change) to highly sensitive( 45% change), which helps in choosing the best-suited cultivars for local cultivation. Higher lipid peroxidation and activity of the ascorbate peroxidase enzyme were major responses to O3 damage, which eventually translated into lower biomass production. The constitutional level of total ascorbate in the leaves was the most important parameter explaining O3 sensitivity among these cultivars. Surprisingly, the role of stomatal conductance was insignificant. These results will guide future breeding efforts towards more O3-tolerant cultivars in China, while strategies for implementing control measures of regional O3 pollution are being implemented. Overall, these results suggest that present ambient O3 pollution is a serious concern for soybean in China, which highlights the urgent need for policy-making actions to protect this critical staple food.     

南京工业区挥发性有机物来源解析及其对臭氧贡献评估

在南京工业区连续测量了2014年5月1日~7月31日和2015年6月1日~7月16日夏季两个高臭氧期的大气中的挥发性有机化合物(VOCs).结合正交矩阵分解(PMF)模型和箱模式(OBM)分析VOCs来源对局部O3生成的贡献.2014年和2015年夏季VOCs浓度平均分别为(36.47±33.44)×10-9和(34.69±34.08)×10-9.PMF模型确定了7种源类别,其中包括汽车尾气、液化石油气(LPG)排放、生物源排放、家具制造业、化工业、化学涂料行业、化学材料工业排放源.在OBM模拟中评估O3与前体物的关系.南京工业区是VOCs控制区,VOCs具有正RIR值,NO的RIR值为负值.烯烃(1.20~1.79)和芳香烃(1.42~1.48)呈现较高的RIR值,控制这两类物种是控制O3浓度最有效的途径.烯烃排放量减少80%时烯烃RIR值达到最高.汽车尾气(1.01~1.11)、液化石油气(0.74~0.82)、生物源排放量(0.34~0.42)和家具制造业(0.32~0.49)是O3形成贡献最大的四大类VOCs来源;减少汽车尾气,生物排放,LPG和家具制造业排放应成为减少局地O3生成最有效策略.     

Effect of exhaust from alcohol fuel on ozone formation in the atmosphere

Alcohols-aldehydes-NO_x-air system smog chamber experiments were undertaken and the reaction model was developed based on the experimental results. Ozone formation behaviors of alcohols and aldehydes were investigated with the computer simulation by changing the ratio of reactants. The effect of alcohol fuel on O₃ formation was estimated. Aldehydes have high reactivity in the atmospheric photochemical reaction. Alcohols can promote O₃ formation substantially under reactive conditions. The efficient control of aldehydes emissions is especially important.     

长江三角洲夏季一次典型臭氧污染过程的模拟

利用WRF/Chem空气质量模式对长江三角洲夏季一次典型臭氧(O3)污染过程的时空分布特征和物理化学机制进行了数值模拟研究.结果表明,模式能够合理地再现这次长江三角洲夏季典型O3污染过程的时空分布特征和演变规律.2013年8月10~18日,长江三角洲主要受副热带高压影响,晴天、高温和小风的气象条件有利于光化学污染的形成.模拟结果表明,长江三角洲地区气象场、地理位置、区域输送和化学生成都对O3的时空分布有影响.敏感性实验表明,上海O3浓度在海洋性气流影响下较低,但上海排放源对长江三角洲O3浓度时空分布的影响较为显著;南京近地面高浓度O3主要贡献为化学生成(烯烃和芳香烃)和高层O3的垂直输送,杭州和苏州近地面高浓度O3主要来源于物理过程.在O3生成速率最大时(11~13h)对O3前体物减排,对长江三角洲15:00的O3峰值浓度影响较为明显.     

臭氧耦合陶瓷膜过滤对膜性能及出水消毒副产物的影响

利用臭氧（O₃）-陶瓷膜过滤（CMF）处理常规工艺出水,研究了不同O₃-CMF耦合方式对膜性能和消毒副产物（DBPs）的影响.结果表明,与单独CMF相比,异位O₃-CMF和原位O₃-CMF均可以有效缓解膜污染,原位O₃-CMF控制效果最佳.异位O₃-CMF对进水（常规工艺出水） DOC去除率（26.25%）略高于原位O₃-CMF（22.31%）,但是其SUVA去除率（83.91%）明显低于原位O₃-CMF（93.10%）.羟基自由基（·OH）生成特征表明原位O₃-CMF可促进O₃产生更多的·OH.在O₃、·OH氧化和陶瓷膜截留协同作用下,异位O₃-CMF和原位O₃-CMF出水中总荧光响应强度和相对分子质量大于0.3×10³,有机物含量降低,进而使得出水中含碳消毒副产物（C-DBPs）生成量分别降低了21.86%和32.35%,含氮消毒副产物（N-DBPs）生成量分别降低了16.16%和19.13%.但O₃和·OH氧化后生成的小分子有机物因难以被CM截留导致其在出水中含量增加,进而增加了卤代酮（HKs）、水合氯醛（CH）和三卤硝基甲烷（THNMs）的产生.本研究对于不同O₃-CMF方式下O₃与CM的协同机制的探讨,改善膜性能和提升DBPs前体物的去除具有一定指导意义.     

A case study of ozone production in a rural area of central ontario

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 NO_x dependence. A minimum value (∼50%) of the contribution was found at a NO_x level of ∼ 6 ppbv for the representative hydrocarbon composition during the episode. At this NO_x level, O₃ production was strongly influenced by the presence of AHCs. At significantly higher or lower NO_x levels, isoprene is more important than AHCs in the local O₃ production.     

Comparison of H2O2 and O3 content in atmospheric samples in the San Bernardino mountains,Southern California

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.     

大气O3浓度升高对2种基因型矮菜豆丛枝菌根(AM)结构及球囊霉素蛋白产生的影响

以臭氧敏感性不同的2种基因型(O3敏感型:S156;O3耐受型:R123)矮菜豆(Phaseolus vulgaris L.)为宿主植物,在模拟的大气臭氧浓度升高环境中研究臭氧胁迫对2种基因型植物的AM结构和球囊霉素蛋白产生的影响,旨在了解大气臭氧浓度升高对AM真菌生长和AM结构形成的影响.结果表明,与自然大气臭氧水平(20 nL.L-1)相比,臭氧浓度升高(70nL.L-1)显著降低了S156和R123植物的菌根侵染率,特别是S156植物,下降了43.6%.臭氧浓度升高明显影响了2种基因型植物的AM结构组成,表现在根室和菌丝室外生菌丝量、单位根长丛枝数的大幅下降,以及根室和菌丝室孢子数的显著增加,特别是S156植物变化更为明显;但2种基因型植物的单位根长泡囊数随臭氧浓度变化不显著.臭氧浓度升高对2种基因型植物的菌根际和菌丝际总球囊霉素蛋白量影响不显著,但导致菌根际和菌丝际的易提取球囊霉素蛋白量大幅增加;不过2种基因型植物间差异不显著.本研究表明,大气臭氧浓度升高显著影响植物菌根侵染率、AM结构形成和易提取球囊霉素蛋白的产生,特别是对臭氧敏感型植物影响更大.     

Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.     

臭氧对有机物混凝的影响

采用PDA(Photometric Disperse Analysis)和有机物表观分子量分级、有机物化学极性分级技术从絮体形成过程、絮体表现、有机物分子水平变化等方面研究了臭氧预氧化对混凝过程的影响;并对比了不同混凝剂在预臭氧条件下的混凝过程和效率.结果表明:臭氧预氧化对混凝过程有复杂的影响,其剂量和水体有机物特征决定了其对混凝的整体影响效果.有机物分级显示,臭氧化对有机物结构有重要影响,导致有机物极性、亲水性组分含量大幅提高(36.7%),小分子量组分(<10×10³)大幅增高(100%左右);但总的DOC去除率不高(3.28%).对PACl而言,在中、低剂量(O₃/TOC<0.7)下,臭氧对絮体形成过程影响较小,但对絮体沉降性和浊度去除已经有阻碍作用.在中、高剂量下(O₃/TOC>0.7),对絮体形成有显著滞后,浊度、有机物去除效率下降.AlCl₃对臭氧化作用反应敏感,臭氧化在试验剂量条件下,对絮体形成和浊度、有机物去除都有明显的阻碍作用.     

Potential bias from non-continuous monitoring of ambient ozone concentrations for characterizing hourly and daily 7- and 12-hour average concentrations

Researchers using chamber experiments to investigate O₃ effects on vegetation do not always monitor O₃ concentrations continuously. Errors introduced because of non-continuous monitoring during experimental treatments may result in the inadequate characterization of hourly average concentrations, with the consequence that summarized exposure indices may provide inaccurate linkages between experimental results and the standard-setting process. We have investigated the uncertainties associated with limited sampling to characterize (1) hourly average and (2) daily 7- and 12-h average O₃ concentrations. As expected, accuracy increased with increased sampling; over- and underestimation of hourly values was directly related to whether the actual concentrations were increasing, decreasing or stable from one hour to the next. When non-continuous sampling was used at sites experiencing small changes from one hour to the next, more than 85 and 60% of the estimated hourly average values were within ±5 and ±2.5 ppb of the actual values, respectively. For a site where average O₃ concentrations changed rapidly from one hour to the next, a greater error was observed. For the daily 7- and 12-h average values, when hourly average concentrations did not change rapidly from one hour to the next, 85% or more of the estimated values agreed within ±2 ppb, independent of sampling frequency. Greater uncertainty was experienced when hourly average concentrations changed at a faster rate. When considering the uncertainties associated with non-continuous sampling, investigators should specify the level of accuracy needed to characterize hourly average concentrations and then select the number of samples per hour required to meet that objective.