2022年春季南京臭氧污染特征及成因分析

2022年春季,受新一轮新冠疫情影响,长三角各城市采取了一系列管控措施,使得大气污染物排放水平降低。对2022年春季(3—5月)南京及长三角地区的六项污染物尤其是臭氧(O₃)的变化特征进行了分析,从气象因素和O₃前体物方面,同时利用基于观测的模型(OBM)对南京O₃污染变化原因进行了研究,并分析了南京挥发性有机物(VOCs)的关键活性组分和来源。结果表明:2022年春季,南京PM_2.5、PM₁₀、NO₂和CO均值浓度均同比下降,但O₃日最大8 h滑动平均质量浓度(O₃-8 h)同比上升19.8%,O₃-8 h超标时间同比增加9 d;长三角区域O₃-8 h同比上升17.9%,O₃-8 h超标天数为2021年同期的2.5倍。南京O₃浓度上升的原因:一方面是由于不利的气象条件,另一方面是由于南京O₃生成处于VOCs控制区,但氮氧化物(NO_x)降幅大于VOCs降幅,同时结合O₃前体物削减方案的分析结果发现,VOCs和NO_x不当的削减比例会导致O₃浓度不降反升。南京O₃生成的关键VOC活性物种依次为乙醛、丙烯、间/对二甲苯、丙烯醛和乙烯;正定矩阵因子分解(PMF)解析结果显示,机动车尾气是南京城区VOCs的主要来源,其次为液化石油气/天然气使用和石油化工。     

Extreme Nitrogen Oxide and Ozone Concentrations in Athens Atmosphere in Relation to Meteorological Conditions

In the present study, we investigate the variation of NO _x (NO + NO₂) and O₃ concentrations and the relation between the extreme events (episodes) of NO _x and O₃ concentrations and the relevant meteorological conditions in the urban atmosphere of the Athens basin. Hourly data of NO, NO₂ and O₃ concentrations from 10 representative monitoring sites located in the Athens basin were used, covering the 10-year time period from 1994 to 2003. The results of our analysis show that the concentrations of air pollutants differ significantly from one monitoring site to another, due to the location and proximity of each station to the emission sources. For each site, there are also significant differences in NO _x and O₃ concentrations from day to day, as well as from month to month and/or from season to season. The annual and seasonal variations show higher NO values in winter and lower in summer. On the contrary, NO₂ and O₃ values are higher in summer (photochemical production of O₃) and lower in winter. These differences are attributed, to a large extent, to the prevailing synoptic and meteorological conditions, the most important between them being the wind direction and speed as well as the atmospheric pressure. Our analysis of the identified 179 extreme NO _x air pollution events shows that most of them took place under anticyclonic conditions, associated with calm or weak winds (speed <2.5 ms⁻¹) of mostly southern to southwestern directions, as well as with low air temperatures and intense stable surface atmospheric conditions. There exists a significant decreasing tendency in NO _x air pollution episodic events over the 10-year study period, resulting in very few to none events in the period from 2000 to 2003. As far as it concerns the extreme O₃ concentrations, 34 air pollution events were identified, occurring under high air temperatures, variable weak winds and intense solar irradiation. The trends of O₃ concentrations are stronger in suburban sites than in urban ones.     

珠三角典型城市COVID-19疫情封闭期间臭氧污染的放大效应研究

珠三角地区臭氧(O₃)已经逐步取代颗粒物成为主要大气污染物。对新型冠状病毒肺炎(COVID-19)疫情封闭期间珠三角城市背景污染效应(特别是对O₃的放大效应)进行了量化研究,发现PM_2.5和NO₂质量浓度均为工作日高于节假日,非疫情期高于疫情期。O₃质量浓度节假日高于工作日,其中疫情期节假日浓度最高。减排会增加低温高湿背景下O₃质量浓度,但会降低其极大值,并导致 O₃随温度和相对湿度的变化梯度减弱。疫情封闭期间异地输送对于局地O₃质量浓度的变化贡献突出。叠加疫情封闭影响的春节假期O₃质量浓度比节前工作日增加20.4%~41.7%,与一般年份特征相反,而NO₂降低65.3%~75.6%,降低程度强于一般年份。疫情封闭期春节期间O₃质量浓度比一般年份上升14.0%~25.9%,而NO₂质量浓度降低37.0%~54.5%。低湿晴好的天气为光化学反应提供有利条件,并且疫情封闭扩大了假期人为源减排规模,导致NO_x质量浓度进一步下降,使其对O₃的滴定效应减弱,同时静稳天气有利于O₃浓度的累积,导致局地O₃污染被逐步放大。     

大连市夏季近地面臭氧污染数值模拟和控制对策研究

通过区域空气质量模型CAMx对大连市2015年8月近地面臭氧(O_3)污染进行模拟,探讨了O_3及其生成前体物(NOx和VOCs)的来源,O_3生成控制区,并根据敏感性分析结果对前体物排放的控制效果进行了定量评估。结果表明:本地NOx排放对大连地区的NOx浓度贡献占90%以上,本地VOCs排放对大连地区的VOCs浓度贡献占80%以上,而本地NOx和VOCs排放对大连地区O_3浓度贡献仅占29%;大连市整体上为VOCs控制区,控制VOCs能有效降低O_3污染,还能有效削减O_3的峰值浓度;通过敏感性分析结果计算得出,削减大连本地工业源VOCs和民用源VOCs能够有效降低大连地区O_3浓度,削减10%的工业源VOCs能使市区O_3平均浓度降低2%左右,削减10%的民用源VOCs能使大连市区平均O_3浓度降低1%左右。建议NOx与VOCs削减比例为1∶2,对大连市O_3和PM2.5污染进行协同控制。     

环境空气质量新标准对珠三角区域站空气质量评价的影响

利用粤港珠三角区域空气质量监控网中天湖、金果湾与万顷沙3个区域站2010年全年SO₂、NO₂、PM₁₀、O₃、PM_2.5与CO自动监测的数据,分析了实施环境空气质量新标准(GB 3095—2012)对这3个子站空气质量评价的影响。研究发现,若采用新标准,万顷沙的NO₂、PM₁₀和PM_2.5年均浓度将不同程度超标。这3个子站空气质量达标率下降7~28个百分点,空气污染指数从91%~99%下降至63%~91%;O₃的引入是导致空气质量达标率下降的最主要的原因;O₃将取代PM₁₀成为最主要的首要污染物,出现频率大于50%,且O₃(8 h)平均浓度的影响大于O₃ (1 h)浓度的影响。PM_2.5的纳入也是导致空气质量达标率下降的重要因素,其超标率为3%(金果湾)~16%(万顷沙)。NO₂标准的收严未对天湖与金果湾空气质量评价造成影响,但导致万顷沙NO₂的超标率从2%上升至10%,且NO₂作为首要污染物的比例达24%。     

Monitoring of Criteria Air Pollutants in Bursa, Turkey

The concentrations of criteria air pollutants such as CO, NO_x (NO + NO₂), SO₂ and PM were measured in the period of May 2001 and April 2003 in the city of Bursa, Turkey. The average concentrations for this period were 1115±1600 μg/m³, 29±50 μg/m³, 51±24 μg/m³, 79±65 μg/m³, 40±35 μg/m³, 98±220 μg/m³, for CO, NO, NO₂, NO_x, SO₂ and PM, respectively. Temporal changes in concentrations were analyzed using meteorological factors. Correlations among pollutant concentrations and meteorological parameters showed weak relations nearly in all data. Lower concentrations were observed in the summer months while higher concentrations were measured in the winter months. The increase in winter concentrations was probably due to residential heating. Pollutants were associated with each other in order to have information about their origin. NO_x/SO₂ ratio was also examined to bring out the source origin contributing on air pollution (i.e., traffic or stationary).     

Fractions and background concentrations of potentially toxic elements in Hungarian surface soils

This work established background concentrations for the pseudo total (HNO₃ + H₂O₂-soluble), mobilisable (NH₄-acetate + EDTA-soluble) and mobile (1?M NH₄NO₃-soluble) element fractions of Hungarian surface soils that can be used as reference values for the soil quality standards. The 193 soils investigated were taken from the Hungarian Soil Information and Monitoring System. The background values for Al, As, B, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn were given as a range covering 95% of the variance of the representative samples. The differences between observed element concentrations and the calculated background values indicated anthropogenic or pedogenic impact in each fraction. The comparison of the calculated background values with the Hungarian quality standards and the contamination limit values of other countries showed that the limit values of a certain region or country are not suitable for other areas. Generally, Mn and Al had the highest, while Cd had the lowest concentration in each fraction. Cr and Al were the least and Sr was the most mobile element. The principal component analysis indicated different geochemical and physico-chemical behaviour of the elements in the fractions; the pseudo total fraction was influenced more by the geological behaviour, while mobilisable and mobile fraction explained a much higher proportion of the total variance of soil physico-chemical properties than soil geochemical properties. The Cd–Ni and Co–Mn element pairs were always in the same principal component in each fractions indicating similar geogenic origin and showing that their solubility changes are similar in function of soil properties.     

Effects of Ageing and Microbial Component on Chemical Availability of 137Cs in a Long-term Experimental Site

A loamy soil contaminated with ¹³⁷CsCl 40 years ago was investigated by a sequential extraction technique to determine the effect of ageing on chemical availability of ¹³⁷Cs. The soil samples were sequentially extracted with H₂O, NH₄Ac, NH₂OH·HCl, H₂O₂, and HNO₃. Extractability of ¹³⁷Cs decreased in the order: HNO₃ > Residual > H₂O₂ > NH₄Ac > NH₂OH·HCl > H₂O. Only 0.94% in labile fractions (H₂O and NH₄Ac), while more than 96% was found in the strongly bound fraction (HNO₃ and residual). However, the activity percentage in labile fractions was increased to 1.34% after autoclaving treatment, while those in the other fractions did not significantly differ. This indicates that the microbial activity played a role in the ¹³⁷Cs retention. In the subsequent pot experiments with ryegrass and leek, specific activities in both plants were significantly higher in autoclaved soil than in non-autoclaved soil, and uptake of ¹³⁷Cs in the five cuts by ryegrass was 25% of the labile ¹³⁷Cs in the soil. In addition, a positive correlation was found between the amount of ¹³⁷Cs in labile fractions and that by plant uptake.     

2018—2021年安徽省PM2.5和O3时空分布特征及其健康风险分析

利用2018—2021年安徽省空气质量监测数据分析了PM_2.5和O₃时空分布特征及其引发的健康风险。结果表明:从时间分布来看,2018—2021年安徽省PM_2.5年均值下降25.5%,而O₃-8 h年均值则保持持平;PM_2.5和O₃-8 h月均值具有明显的季节变化特征,PM_2.5月均质量浓度和超标天数均在冬季达到最大值,O₃-8 h月均值和超标天数则在夏季达到最大值。从空间分布来看,PM_2.5、O₃-8 h年均值和超标天数均为皖北最高,其次为皖中,最后为皖南。夏季O₃是主要的健康风险因子,冬季PM_2.5是主要的健康风险因子。当PM_2.5超标时,除2021年皖北地区外(PM₁₀是主要的健康风险因子),PM_2.5均是主要的健康风险因子;当O₃-8 h超标时,O₃是主要的健康风险因子。     

Study of urban atmospheric pollution in Navarre (Northern Spain)

An ambient air quality study was undertaken in two cities (Pamplona and Alsasua) of the Province of Navarre in northern Spain from July 2001 to June 2004. The data were obtained from two urban monitoring sites. At both monitoring sites, ambient levels of ozone, NO_x, and SO₂ were measured. Simultaneously with levels of PM₁₀ measured at Alsasua (using a laser particle counter), PM₁₀ levels were also determined at Pamplona (using a beta attenuation monitor). Mean annual PM₁₀ concentrations in Pamplona and Alsasua reached 30 and 28 μg m⁻³, respectively. These concentrations are typical for urban background sites in Northern Spain. By using meteorological information and back trajectories, it was found that the number of exceedances of the daily PM₁₀ limit as well as the PM₁₀ temporal variation was highly influenced by air masses from North Africa. Although North African transport was observed on only 9% of the days, it contributed the highest observed PM₁₀ levels. Transport from the Atlantic Ocean was observed on 68% of the days; transport from Europe on 13%; low transport and local influences on 7%; and transport from the Mediterranean region on 3% of the days. The mean O₃ concentrations were 45 and 55 μg m⁻³ in Pamplona and Alsasua, respectively, which were above the values reported for the main Spanish cities. The mean NO and NO₂ levels were very similar in both sites (12 and 26 μg m⁻³, respectively). Mean SO₂ levels were 8 μg m⁻³ in Pamplona and 5 μg m⁻³ in Alsasua. Hourly levels of PM₁₀, NO and NO₂ showed similar variations with the typically two coincident maximums during traffic rush hours demonstrating a major anthropogenic origin of PM₁₀, in spite of the sporadic dust outbreaks.     

Field Survey of Trans-boundary Air Pollution with High Time Resolution at Coastal Sites on the Sea of Japan during Winter in Japan}

An intensive field survey, with 6-h measurement intervals, of concentrations of chemical species in particulate matter and gaseous compounds was carried out at coastal sites on the Sea of Japan during winter. The concentration variation of SO₂(g) and HNO₃(g) were well correlated, whereas the NH₃(g) concentration variation had no correlation with those of SO₂(g) and HNO₃(g). The NH₄ ⁺ (p)/non-sea-salt- (nss-)SO₄ ^{2 −}(p) ratio in particulate matter was mainly affected by the location of the sampling site. One or more concentration peaks of nss-Ca^{2 +} for survey period were observed. Backward trajectories analyses for the highest nss-Ca^{2 +} concentration peaks showed some inconsistency in pathways. We consider that insufficient mixing of the atmosphere and/or insufficient time for the transported air pollutants to react with those discharged locally are the most likely explanations for the discrepancies between the measured products [HNO₃][NH₃] and the calculated values.     

Using Measurements of Nitrogen Oxides to Estimate the Emission Controls Required to Meet the UK Nitrogen Dioxide Standard

In this paper we introduce a new method of analysing the relationship between nitrogen dioxide (NO₂) and oxides of nitrogen (NO_x) concentrations using data from the UK National Air Quality Archive. The study includes analyses of measurements from two different types of site in London, a kerbside site: Cromwell Rd, and three background sites: Bridge Place, London Bloomsbury and West London, over several years (1991–7). The data in some years showed that hourly NO₂ concentrations exceeded the UK Standard of 150 ppb. Data were binned, averaged, and polynomials fitted at each site. Analysis of the resulting polynomials was used to estimate reductions in NO_x emission required to achieve the National Air Quality Strategy Objective. Examination of the empirical ratio NO₂:NO_x (the 'yield') gives an indication of the sensitivity of the NO₂ to NO_x controls and the amount of NO₂ that would arise from modelled values of total oxides of nitrogen. The response of NO₂ to emission changes is very non-linear, implying 30–45% controls on NO_x may be required.     

Modifications of the transition flow reactor theory for the more accurate measurement of nitric acid and nitrate and ammonium ions

Sixty five samples were taken with a Transition Flow Reactor (TFR) for the measurement of nitric acid (HNO₃) and nitrate particulates (NO ₃ ⁻ ), in a central Athens street having a heavy traffic density, between February 1989 and February 1990. It was established that the TFR theory overestimated HNO₃ and underestimated NO ₃ ⁻ . This is caused by the retention of a fraction of the NO₂ and a fraction of the HNO₂ as NO ₂ ⁻ on the sampler's nylon linear. NO ₂ ⁻ is in turn oxidized to NO ₃ ⁻ and this is determined as HNO₃. Two modifications of the TFR theory are proposed for a better estimation of the HNO₃ and NO ₃ ⁻ . With the first modification HNO₃ is estimated as being equal to the smaller of two values: HNO_{3 TFR} and the value calculated if it is considered that 91% of HNO₃ is retained by the nylon filter. The second modification was based on the quantification of the effect of NO₂ on the concentrations of HNO₃ and NO ₃ ⁻ . This modification is an improvement on the first one and enables the calculation of a lower limit for the concentration of HNO₂. Both modifications improve the accuracy of the TFR sampler in measuring HNO₃ and NO ₃ ⁻ , without altering it structurally. It was also found that the nylon filter partially retains some NH₃, causing a negative error in the measurement of NH ₄ ⁺ with the TFR. The extent of NH₃ retention on the nylon filter is proportional to the HNO₃ concentration. This error must be taken into account whenever NH ₄ ⁺ is being determined.     

Evaluation of trace element contents of some herbal plants and spices retailed in Kayseri,Turkey

The trace element contents of seven kinds of herbal plants and spice samples retailed in local markets in Kayseri-Turkey were determined by flame atomic absorption spectrometry after digestion with HNO₃/H₂O₂ mixture. The concentration ranges for the studied elements were found as 6.0–15.2, 0–32.2, 80.0–324.8, 8.1–386.3, and 13.1–36.2 μg/g for copper, nickel, iron, manganese, and zinc, respectively. The levels of cobalt, lead, and chromium ions in all the investigated samples were found to be below the detection limit of flame atomic absorption spectrometry. The results found in the present work were compared with values in the literature.     

Fractionation and potential mobility of trace metals in Danube alluvial aquifer within an industrialized zone

Thirty-five alluvial sediments of the River Danube and 12 groundwater samples were taken within the Pan?evo Oil Refinery (Serbia). The results for groundwater samples exceed European primary drinking water standards for Fe (obtained results, >200 μg/l) and Mn (obtained results, >50 μg/l), while the levels of the trace metals are below the thresholds for drinking water quality. Sediments were treated by sequential extraction procedure with five different solutions, each having a higher extraction capacity than the previous one. We also wanted to determine the possible relationships among trace metals and between sediment properties and elemental concentrations. These solutions partitioned metals into CH₃COONH₄ extractable (F1); HCl carbonate extractable and NH₂OH·HCl easily reducible (F2); (NH₄)₂C₂O₄/H₂C₂O₄ moderately reducible (F3); H₂O₂–HNO₃ organic/sulfide extractable fractions (F4); and HCl acid-soluble residue (F5). The sum of trace metals Ni, Pb, Cu, and Zn associated with the first two fractions (exchangeable, carbonate, and easily reducible) is significant and extremely important because it represents the proportion of heavy metals that can be easily remobilized by changes in environmental conditions such as pH, redox potential, salinity, etc. Sediments located nearer the groundwater flow are exposed to stronger groundwater fluctuation and had a higher quantity of amorphous and less stable substrates of trace metals. Principal component analysis was used to understand and visualize the associations between the trace metals and certain geological forms within analyzed sediments. The observed association between Cr with total sulfur and Mn from the acid-soluble residue could indicate that Cr is in the form of reduced, less toxic Cr(III), which is from the ecochemical point of view very important.     

The impact assessment of Diwali fireworks emissions on the air quality of a tropical urban site, Hyderabad, India, during three consecutive years

Diwali is one of the largest festivals for Hindu religion which falls in the period October–November every year. During the festival days, extensive burning of firecrackers takes place, especially in the evening hours, constituting a significant source of aerosols, black carbon (BC), organics, and trace gases. The widespread use of sparklers was found to be associated with short-term air quality degradation events. The present study focuses on the influence of Diwali fireworks emissions on surface ozone (O₃), nitrogen oxides (NO _x ), and BC aerosol concentration over the tropical urban region of Hyderabad, India during three consecutive years (2009–2011). The trace gases are analyzed for pre-Diwali, Diwali, and post-Diwali days in order to reveal the festivity’s contribution to the ambient air quality over the city. A twofold to threefold increase is observed in O₃, NO _x , and BC concentrations during the festival period compared to control days for 2009–2011, which is mainly attributed to firecrackers burning. The high correlation coefficient (~0.74) between NO _x and SO₂ concentrations and higher SO₂/NO _x (S/N) index suggested air quality degradation due to firecrackers burning. Furthermore, the Cloud–Aerosol Lidar and Infrared Pathfinder Satellite Observation-derived aerosol subtyping map also confirmed the presence of smoke aerosols emitted from firecrackers burning over the region. Nevertheless, the concentration level of pollutants exhibited substantial decline over the region during the years 2010 and 2011 compared to 2009 ascribed to various awareness campaigns and increased cost of firecrackers.     

试点城市O3浓度特征分析

利用2009年O3试点城市的03监测数据,分析了北京、天津、上海、青岛、沈阳和广东的03浓度变化特征,统计了年超标情况,并结合气象要素数据分析了其对03浓度的影响.结果表明,不同城市各点位间03浓度变化趋势基本一致,但因点位类型不同,浓度存在差异;O3浓度呈单峰型日变化,在13:00-15:00出现最大值,6:00-7:00出现最小值;O3超标主要集中在4-8月份,广州和北京超标现象较多;O3浓度受温度、降水、风速和风向等气象要素影响较大.     

大气硝酸测量方法研究进展

大气中硝酸(HNO3)的生成是排放到空气中氮氧化物(NOx)的主要沉降途径,对降水酸化、二次细颗粒物中硝酸盐的形成以及在研究光化学污染和霾形成等大气复合污染过程之间的联系中具有重要作用.获得高时间分辨率、准确的大气HNO3测量数据对研究和认识大气中NOx的循环机理是十分必要和迫切的.大气中的HNO3浓度低且具有很强的吸...     

Photocatalytic degradation of NOx in a pilot street canyon configuration using TiO2-mortar panels

Titanium dioxide is the most important photocatalysts used for purifying applications. If a TiO₂- containing material is left outdoors as a form of flat panels, it is activated by sunlight to remove harmful NOx gases during the day. The photocatalytic efficiency of a TiO₂-treated mortar for removal of NOx was investigated in the frame of this work. For this purpose a fully equipped monitoring system was designed at a pilot site. This system allows the in situ evaluation of the de-polluting properties of a photocatalytic material by taking into account the climatologic phenomena in street canyons, accurate measurements of pollution level and full registration of meteorological data The pilot site involved three artificial canyon streets, a pollution source, continuous NOx measurements inside the canyons and the source as well as background and meteorological measurements. Significant differences on the NOx concentration level were observed between the TiO₂ treated and the reference canyon. NOx values in TiO₂ canyon were 36.7 to 82.0% lower than the ones observed in the reference one. Data arising from this study could be used to assess the impact of the photocatalytic material on the purification of the urban environment.     

辛集市"十三五"期间空气质量特征分析

重点对河北省辛集市"十三五"期间整体空气质量变化情况以及影响辛集市优良天数的2个重要参数O₃和PM_2.5的污染规律进行了分析。结果表明,辛集市"十三五"期间空气质量改善明显,优良天数整体增加,污染天数整体减少。O₃浓度及其作为首要污染物出现的天数整体呈现上升趋势,对综合指数的贡献率逐年增加;O₃污染高发期主要集中在4—9月,高值区域分布差距较大,但市区污染持续突出。PM_2.5浓度逐年下降,以PM_2.5为首要污染物的天数逐年减少;PM_2.5浓度季节变化特征整体呈现"秋冬高、春夏低"的分布特点,空间分布呈"南北高、中间低"的污染特征。