动态校准仪臭氧间接传递技术

对5台主流动态校准仪开展臭氧间接传递技术研究,对动态校准仪的准确性、可靠性、稳定性及臭氧传递的线性方程等性能参数进行了实验室考察。总体而言,发生型动态校准仪和分析型动态校准仪均可用于臭氧传递工作中。分析型动态校准仪可直接进行臭氧传递,发生型动态校准仪在臭氧传递前必须进行预校准。建议至少每3个月对发生型动态校准仪进行1次臭氧传递,每6个月对分析型动态校准仪进行1次臭氧传递。     

紫外光度法臭氧自动监测仪及其标准传递方法

随着我国经济的快速增长和城市化进程的不断加速,以臭氧为主的光化学污染问题已成为大气环境保护领域关注的重点、热点问题。对臭氧进行自动监测是环境管理和科学研究的需要,文中介绍了臭氧自动监测仪和臭氧量值溯源体系,重点探讨了臭氧监测干扰因素及标准传递方法,并通过实验比较验证了带光度计的臭氧校准仪具有较好的输出稳定性。     

臭氧监测仪实验室校准及稳定性测试

以国内监测系统在用的臭氧校准仪为二级传递标准对臭氧监测仪开展了实验室校准,通过计算单次校准所得校准曲线的斜率和截距,符合中国相关标准中关于臭氧监测仪的校准指标:多点校准所得校准曲线的斜率为0.95~1.05,截距为-5~5 nmol/mol。进一步对2台臭氧监测仪进行了稳定性测试,12个月内臭氧监测仪的斜率变化为0.976 05~1.008 42,截距变化为-0.669 00~0.577 93 nmol/mol,臭氧监测仪的斜率、截距均符合臭氧监测仪校准指标的要求。稳定性测试表明,TF 49i型臭氧监测仪和EC 9810型臭氧监测仪经校准后均可用于实验室内臭氧标准传递比对工作。实验中臭氧监测仪更换臭氧涤除器、仪器零件后校准曲线的斜率均有明显变化,建议更换耗材后需采用高浓度臭氧对臭氧监测仪进行饱和并再次校准。     

二氧化氮标准物质校准氮氧化物分析仪的差异性

采用一氧化氮、二氧化氮标准物质对化学发光法的氮氧化物分析仪进行校准,并分析校准系统中零气源、连接管路、动态气体校准仪和标准物质对二氧化氮校准的影响,发现一氧化氮标准物质中的二氧化氮杂质会影响氮氧化物的校准结果,得出氮氧化物分析仪校准需要进行二氧化氮补偿的结论;同时,通过比较国产二氧化氮和进口二氧化氮标准物质产生的校准结果,得出进口二氧化氮标准物质较国产二氧化氮标准物质的稀释结果具有更好的稳定性和一致性。     

衡阳市区和衡山背景站臭氧浓度变化规律的对比分析

选取衡阳市区和衡山背景站臭氧自动监测数据,分析两地的臭氧污染特征。对空气质量的优良率情况、臭氧作为首要污染物的变化情况、臭氧浓度的日变化特征、典型时段的浓度变化特征、臭氧浓度的月际变化特征和臭氧与PM_(2.5)的关联情况等进行了分析。结果表明,多云及阴雨天气时,衡阳市区的臭氧浓度日变化幅度大于衡山背景站。夏季,衡阳市区和衡山背景站的臭氧浓度的日变化特征规律差异较大,臭氧浓度分布比较分散,前者为典型的单峰形,后者则波动平缓。冬季,日变化幅度不大,但衡阳市区的臭氧浓度明显低于衡山背景站。衡山背景站和衡阳市区的臭氧基本同步变化,但日均值高于衡阳市区。     

2008-2016年臭氧监测试点城市的臭氧污染特征

选取臭氧试点城市北京、沈阳、上海和重庆，通过对2008-2016年臭氧监测数据进行分析研究，可以看出4个试点城市中北京的臭氧污染最严重。4个城市的臭氧污染特征均为高浓度臭氧所占比例较大，高值比较高，低浓度臭氧所占比例较小。北京、沈阳和上海的年平均臭氧浓度总体呈上升趋势。北京、上海、重庆、沈阳4个城市9年的超标天数比例分别为15.9%、7.7%、3.9%、6.5%。上海的臭氧浓度在秋季非常高。2012年的臭氧变化趋势比较异常，可能是由于2012年发生的不寻常气候条件导致。4个城市的臭氧浓度变化和气象条件的变化显著相关。     

沈阳环境空气臭氧浓度及累积速率时序曲线模拟研究

为了解环境空气臭氧累积规律,利用2017年沈阳市环境空气臭氧浓度数据,统计分析臭氧累积速率,并利用回归方法拟合并优化臭氧浓度及其累积速率的时间序列模型,同时结合气温、风力、臭氧前体物等时序变化情况分析臭氧浓度的影响因素。研究发现:沈阳市臭氧月均浓度年变化、日均浓度年变化以及小时浓度日变化时序曲线均呈现单峰形态;年变化中,6月的臭氧浓度最大,4月臭氧累积速率达到最大值;日变化中,14:00臭氧浓度达到最大值,09:00—11:00臭氧累积速率最大,19:00—20:00臭氧迅速消减。温度、风速同臭氧浓度之间均有较好的正相关性。臭氧前体物二氧化氮、挥发性有机物与臭氧浓度之间均呈明显的负相关性。     

南京市典型臭氧污染过程的激光雷达垂直观测解析

利用臭氧激光雷达对南京市一次典型臭氧污染过程连续观测,分析该典型臭氧污染过程中近地面和高空臭氧的变化规律、污染的发生过程与成因。结果表明:在夏季高温、风速低、冷空气影响锋前的静稳天气下,近地面臭氧的循环生成和夜间高空残留的臭氧在湍流作用下混合并积累造成该污染过程;近地面和低层臭氧浓度具有明显的日变化趋势,单峰型特征,而高空臭氧浓度无明显日变化特征,夜间维持高值;边界层高度上下始终存在臭氧高值带,厚度达数百米;正午至午后时段,各垂直高度上臭氧浓度混合均匀,随高度基本无梯度变化,达到近地面至高空1.5 km的臭氧高污染层覆盖。     

新疆玛纳斯县大气臭氧浓度时空变化及影响因子分析

选取新疆玛纳斯县2018—2019年空气自动站的监测数据,统计分析了臭氧浓度时空变化规律。主要结果表明,2019年臭氧为首要污染物天数同比2018年增加48.9%,2019年因臭氧浓度超标造成轻度污染天数较上年增加250%,臭氧已成为影响空气质量的重要因子之一。臭氧浓度具有明显的季节变化特征,2018—2019年玛纳斯县臭氧平均浓度均在5—8月达到全年的最高值,11月至翌年1月浓度为全年最低值,臭氧浓度整体呈现夏季高,冬季低的特点,城市形成局部臭氧超标的主要原因及其影响力的大小受温度和风速的影响。在此基础上对臭氧污染进行了溯源及影响因子分析,提出防控臭氧污染的建议。     

杭州市臭氧污染特征及过程分析

利用2013—2016年杭州市国控点臭氧观测资料,讨论了杭州市臭氧时空变化特征,并对一次臭氧高浓度过程进行分析。结果显示,近年来杭州市臭氧浓度以10. 3%的升幅渐增,增幅大于北京、上海、广州等城市。千岛湖背景点及位于城区的朝晖五区、下沙、西溪站点臭氧浓度月变化存在2个峰值,第一峰值出现在5月,受降水、温度影响次峰值出现在8—10月;夜间臭氧浓度背景点高于城区点。杭州市10个国控站点臭氧浓度相对标准偏差逐年减小,臭氧污染已呈区域性,城东为重污染区域。2015年8月出现的一次臭氧重污染过程主要是受副热带高压控制下和台风外围的影响,导致杭州市朝晖五区站点臭氧浓度高达228μg/m~3,台风登陆后得以缓解。     

湖北臭氧分布特征及其管控措施

采用地面站点观测、卫星观测以及UWCM 0-D箱子模型模拟的方法研究湖北2013—2015年臭氧时空分布特征,并探讨其管控措施。从地面站点观测看出,时间分布上,这3年臭氧年平均浓度经历先下降后上升的过程,总体呈上升趋势,而二氧化氮年平均浓度则呈现持续下降的趋势;空间分布上,湖北各区域臭氧浓度分布不均匀,呈现东高西低的递减分布趋势。从卫星观测数据看出,2015年湖北的臭氧柱浓度高于2013、2014年同期。从空间分布来看,臭氧的柱浓度是从东北到西南、从省外到省内逐渐递减,因此推测,除了本地生成,湖北的臭氧有一部分是来源于省外传输。最大臭氧生成量法显示,烯烃(乙烯和丙烯)对湖北夏天臭氧生成量的贡献远大于其他挥发性有机化合物。箱子模型模拟的结果显示,湖北应该通过控制挥发性有机化合物的排放来降低臭氧生成速率,控制氮氧化物反而使臭氧生成速率提高。     

Ozone Exposures and Implications for Vegetation in Rural Areas of the Central Appalachian Mountains, U.S.A.

The United States is making the transition from the 1979 1 hr maximum ozone standard to the newly adopted 8 hr ozone standard (3 yr average of the 4th highest maximum 8 hr ozone concentration). Consequently, we analyzed and compared ozone concentrations under both standards from a variety of monitoring sites throughout the central Appalachian region of Kentucky (KY), West Virginia (WV), and Virginia (VA). Data from 1988-1999 were used to determine how ozone exposure between the two metrics compared for remote sites. Most sites exceeded the 1 hr standard in 1988-1990 due to the 3 yr averaging and multiple high ozone concentrations that occurred over the region in 1988. All sites were in compliance with the 1 hr standard every year after 1991. It was much more common for the ozone exposure to exceed the 8 hr standard, particularly from 1997-1999. Many sites showed exceedences beginning in 1995; Big Meadows (VA) exceeded the 8 hr standard all years except 1994 and 1996. Response of vegetation to ozone in these areas was determined using the combination of W126 values (sigmoidally weighted exposure index), the number of hours that average concentrations > or = 0.10 ppm (N100), and the presence of moderate or more extreme droughts. In general, W126 and N100 values suggested that negative vegetation growth responses over most of the 12 yr would have been minimal for most sites, even for those exceeding ozone standards. Drought-induced stomatal closures would have overridden more extreme negative growth responses at all but the Big Meadows site in 1988.     

Prediction of extreme ozone levels in Barcelona, Spain

Barcelona is one of the most polluted cities in Western Europe, although our levels of air pollution are within the World Health Organisation air quality guidelines. However, high concentrations of air pollution have not been studied yet. Ground ozone levels is a topic of considerable environmental concern, since excessive level of ozone are taken as indicative of high pollution. In terms of the air quality guidelines ozone levels higher than 100 µg m^–3 can start to be health-hazards for human health. Our objective is to report a detailed analysis of ozone data exceeding the thresholds established by the air quality guidelines. Data analysed were collected in two measurement stations in Barcelona, for the reference period 1991–1996. Applying statistical techniques commonly used in the analysis of extreme values, mainly the Peak Over Threshold method was used for in this study. The analysis reveal that the ozone threshold values for the protection of human health has exceeded many times in both stations. The estimated return values for 3, 10, and 40 yr exceed the threshold value for information to the public of almost once in both stations, also it seems to be unlikely that the threshold value for warning to the public will be exceeded in 40 yr.     

Monitoring of the Endangered Pinna nobilis Linné, 1758 in the Mar Grande of Taranto (Ionian Sea, Italy)

Two methods were used to calculate the meteorologically adjusted ground level ozone trends in southern Taiwan. The first method utilized is a robust linear regression method. The second approach uses a multilayer perceptron (MLP) artificial neural network (ANN) method. The observations obtained from 16 monitoring stations were analyzed and divided into six groups by hierarchical divisive clustering procedure. The daily maximum 1 and 8 h ozone concentrations for each group are then calculated. The meteorologically adjusted trends obtained by linear regression and MLP methods are smaller than the unadjusted trends for all groups and average time. It indicts that the meteorological conditions in Taiwan tend to increase ambient ozone concentrations in recent years.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

Trends analysis of ambient 8 hour ozone and precursor monitoring data in the south central U.S

For the south central U.S., lower tropospheric ozone pollution has been a persistent and challenging problem. This paper provides long-term trends analyses of the ozone and precursor monitoring data collected over the past 20 years in four south central U.S. cities. The results of these analyses should be useful to air quality scientists, managers, planners, and modelers in assessing the effectiveness of ozone pollution control strategies being implemented or being planned for the future. Results of the data analyses show that all areas have monitored significant decreases in ozone and precursor concentrations over the past 20 years, especially in El Paso, Texas. Continuing challenges include the reduction of the percentage of time that monitors record 8 hour ozone concentrations over the U.S. 8 hour ozone standard, and the future control of highly reactive volatile organic compounds.     

A New All Season Passive Sampling System for Monitoring Ozone in Air

A new all season passive sampling system for monitoring O₃ in the atmosphere has been developed in the laboratory and validated in the field. The unique features for this system include a newly designed passive sampler and a rain shelter, which allow the passive sampler to be installed in the field facing downwards. An equation associated with meteorological parameters is used to calculate the passive sampling rates. This system has been extensively tested in the lab (temperature from –18 to 20°C, relative humidity from 13 to 81%, and wind speed from 0.5 to 150 cm/s) and validated in the field in climates of all seasons. The accuracy of the ozone concentrations in the atmosphere obtained with the use of the new passive sampling system was higher than 85% compared to those obtained with continuous ozone analyzers. The new ozone passive sampling system can be used to measure ambient O₃ concentrations ranging from 3 ppb to 1000 ppb based on one-day exposure and 0.1 ppb to 140 ppb for a monthly exposure period. It is also reasonable to conclude that the new passive sampling system can be used for eight-hour exposure study because of the low field blanks and high sampling rates.