基于KZ滤波法的河北省PM2.5和O3浓度不同时间尺度分析研究

大气细粒子和臭氧是影响我国城市空气质量的主要污染物质,其浓度的大小不仅与污染源的排放量有关,气象条件也是影响其浓度分布特征的重要因素.要评估污染物减排措施的效果,有必要将气象条件的影响剥离出来,仅评估排放量的降低对污染物浓度长期变化趋势的影响.本文使用KZ(Kolmogorov-Zurbenko)滤波方法对河北省石家庄、保定、张家口三市2013—2017年PM_(2.5)和O_3逐日浓度时间序列进行分解,并使用同期地面气象观测数据对各时间序列进行逐步回归分析,将经过KZ滤波后的长期序列与经逐步回归后的结果的差值再次进行滤波处理,得到去除气象影响的污染物浓度长期变化趋势,该浓度仅与污染物的排放量有关.结果表明,因污染源排放的影响,河北省三市大气PM_(2.5)浓度在研究年内除在2017年初略有上升以外,其余季节均呈下降趋势.河北省三市大气O_3浓度在研究年内均有波动上升趋势.气象条件对PM_(2.5)浓度长期变化趋势的影响大于O_3.     

Lake Michigan Ozone Study (LMOS): Measurements from an instrumented aircraft

As part of the Lake Michigan Ozone Study, the NOAA instrumented King Air research aircraft made a series of flights over Lake Michigan during the summers of 1990 and 1991 to characterize the atmospheric conditions prevailing during times when O₃ concentrations exceeded the air quality standard. Most of the time, O₃ concentrations were within the normal range (40–70 ppbv) for the location and season, but higher concentrations were measured during the afternoon flights at several isolated locations. During three afternoon flights, high O₃ concentrations (> 120 ppbv) were observed along portions of the flight path; the highest 1-min average exceeded 160 ppbv. In two flights the highest O₃ concentrations were observed in the lower boundary layer over the eastern portion of the flight track; in one case the high concentrations were found over the western side of the lake throughout the boundary layer. The increased O₃ was accompanied by moderately increased SO₂ and NO_x (10–20 ppbv); outside the region of elevated O₃, the SO₂ and NO_x were less than 2–3 ppbv. The elevated zone concentrations were related to emissions from the urban region located near the southern and southwestern shores of Lake Michigan.     

基于轻量级梯度提升机的南京大气臭氧浓度预测

采用南京地区2015年1月至2016年12月期间的空气质量数据和常规气象资料数据,分析了南京地区O₃浓度变化特征,建立基于轻量级梯度提升机(LightGBM)的O₃浓度预测模型,并将该模型与支持向量机、循环神经网络和随机森林等3种在空气质量预测方向上常用的机器学习方法进行了对比,验证模型的有效性和可行性.结果表明,南京地区O₃浓度变化具有显著的季节性差异,浓度变化受前期浓度、气象因子和其他空气污染物浓度的共同影响.LightGBM模型较为准确地预测了南京地区地面O₃浓度(R²=0.92),且该模型的预测精度和计算效率等性能优于其他模型.尤其是在容易出现臭氧污染的高温天气,该模型预测准确性明显高于其他模型,模型稳定性较好.LightGBM具有预测准确度高、稳定性好、有良好的泛化能力和运算时间短等特点,在O₃浓度预测方面具有显著的优势.     

O3/UV反应体系的有机物消解动力学模型

为了提高O₃/UV（臭氧协同紫外）反应体系对有机物的消解效率,降低能源消耗,基于O₃分解的SHB机理和O₃、有机物在紫外辐射下的光解机理,并考虑该反应体系中存在的3种可能的有机物消解途径和反应器出口处O₃气体浓度变化,建立了O₃/UV反应体系的动力学模型.将该模型用于消解过程中有机物消解率变化规律的研究,进一步优化消解工艺参数.结果表明:使用苯酚和乙酸作为目标有机物,以该模型进行仿真,从理论上验证了O₃气体浓度与紫外辐射间存在协同作用和不同工艺参数下所建立模型的灵敏性;将该模型与其他模型、试验测量值进行对比,验证了其优越性和准确性;对比不同pH下的3种消解途径各自贡献率的仿真结果,发现O₃/UV反应体系的pH对其消解有机物效率具有重要影响.研究显示:在O₃/UV反应体系中,紫外辐射强度和投加的O₃气体浓度二者间具有协同作用,同时调节可获得更好的消解效果;在酸性条件下有机物消解以O₃直接氧化为主,碱性条件下则以自由基间接氧化为主.      

Calculation of long term averaged ground level ozone concentrations

Seasonal averaged ground level concentrations for O₃ have been calculated for The Netherlands by means of a two-layer Lagrangian long-range transport (LRT) model. The model includes emissions, nonlinear atmospheric chemistry, dry deposition, exchange between boundary layer (BL) and free troposphere (FT) and fumigation between a mixed layer and an aged smog layer. Concentrations of primary and secondary pollutants in the FT are obtained from a two-dimensional global model developed by Isaksen.In the reference calculation the modelled concentrations of Ox (sum of O₃ and NO₂) and O₃ are in fair agreement with measurements. The NO_x (sum of NO and NO₂) and NO₂ concentrations are under-estimated by the model but there is a good temporal correlation between calculated and measured concentrations. Validation of other components involved in the chemical scheme is hardly possible due to the paucity of measured data. It can only be stated that the results presented in this paper are not in disagreement with measured or modelled data presented in the literature.In a number of sensitivity runs the influence of European anthropogenic emissions of NO_x and volatile organic compounds (VOC) has been investigated. The calculations indicate that the influence of European emissions on the growing season, daytime averaged (May–September, 10–17 h) O₃ concentrations in The Netherlands is small. For European reductions in the order of tens of per cents a VOC emission reduction is more effective than a NO_x emission reduction in lowering the O₃ concentrations. For strong reductions (about 70%) VOC and NO_x are equally effective. The effects of the modelled underprediction of NO_x concentrations on the production of O₃ on a European scale are probably small. On a local scale the effects are more pronounced due to the NO/O₃ titration (photostationary equilibrium). Therefore, an empirical correction is applied on the modelled O₃ concentrations. After this correction, it is shown that daytime O₃ levels during the growing season increase when European NO_x emissions are reduced (2.0–7.7.% increase at 50% NO_x emission reduction). A reduction in VOC emission leads to decreasing O₃ levels (9% reduction for 40% VOC emission reduction, 16% reduction for 70% VOC emission reduction). For a combined reduction of both VOC and NO_x slightly decreasing ground level O₃ concentrations are expected.     

Evidence of aircraft activity impact on local air quality: A study in the context of uncommon airport operation

Wuhan Tianhe International Airport (WUH) was suspended to contain the spread of COVID-19, while Shanghai Hongqiao International Airport (SHA) saw a tremendous flight reduction. Closure of a major international airport is extremely rare and thus represents a unique opportunity to straightforwardly observe the impact of airport emissions on local air quality. In this study, a series of statistical tools were applied to analyze the variations in air pollutant levels in the vicinity of WUH and SHA. The results of bivariate polar plots show that airport SHA and WUH are a major source of nitrogen oxides. NO_x, NO₂ and NO diminished by 55.8%, 44.1%, 76.9%, and 40.4%, 33.3% and 59.4% during the COVID-19 lockdown compared to those in the same period of 2018 and 2019, under a reduction in aircraft activities by 58.6% and 61.4%. The concentration of NO₂, SO₂ and PM_2.5 decreased by 77.3%, 8.2%, 29.5%, right after the closure of airport WUH on 23 January 2020. The average concentrations of NO, NO₂ and NO_x scatter plots at downwind of SHA after the lockdown were 78.0%, 47.9%, 57.4% and 62.3%, 34.8%, 41.8% lower than those during the same period in 2018 and 2019. However, a significant increase in O₃ levels by 50.0% and 25.9% at WUH and SHA was observed, respectively. These results evidently show decreased nitrogen oxides concentrations in the airport vicinity due to reduced aircraft activities, while amplified O₃ pollution due to a lower titration by NO under strong reduction in NO_x emissions.     

Air pollutant concentrations in Varanasi,India

This study reports the diurnal patterns in the concentrations of ozone (O₃), nitrogen dioxide (NO₂), sulphur dioxide (SO₂) and total suspended particulate matter (TSP) in the urban atmosphere of Varanasi city in India during 1989. The city was divided into five zones and three monitoring stations were selected in each zone.Ambient concentrations of NO₂ and SO₂ were maximum during winter but ozone and TSP concentrations were highest during summer. The measured maximum concentrations (2-h average) were 150 and 231 μg m⁻³ (0.078 and 0.086 ppm) for NO₂ and SO₂, respectively, for the winter season. Ozone and TSP concentrations reached a maximum of 160 (0.08 ppm) and 733 μg m⁻³, respectively, in the summer. NO₂ and SO₂ concentrations peaked in the morning and evening. Peak concentrations of O₃ occurred in the afternoon, generally between noon and 4 p.m. Maximum concentrations of O₃, NO₂, SO₂ and TSP were measured in zones I and II, and minimum in zone V.     

A characterization of the spatiotemporal variability of non-urban ozone concentrations over the eastern United States

The spatial and temporal variability of the daily 1-h maximum O₃ concentrations over non-urban areas of the eastern United States of America was examined for the period 1985–1990 using principal component analysis. Utilization of Kaiser's Varimax orthogonal rotation led to the delineation of six contiguous subregions or “influence regimes” which together accounted for 64.02% of the total variance. Each subregion displayed statistically unique O₃ characteristics and corresponded well with the path and frequency of anticyclones. When compared to the entire domain, the mid-Atlantic and south subregions observe higher mean daily 1-h maximum concentrations. Concentrations are near the domain average for the northeast and southwest subregions and are lowest in the Great Lakes and Florida subregions. The percentage of observations exceeding 120 ppb were greates in the mid-Atlantic and southwest subregions, near the domain average in the northeast and south subregions, and lowest in the Great Lakes and Florida subregions.Examination of the time series of the principal component scores associated with the subregions indicated that Great Lakes and mid-Atlantic subregions tend to observe a stronger seasonal cycle, with maximum concentrations occurring during the last week in June and first week in July, respectively. The strength of this seasonality is weakened for the northeast and south subregions and its timing delayed, until the end of July and the first of August, respectively. The southwest subregion experiences a greatly diminished seasonality, with maximum concentrations delayed until the middle of August. The seasonality found in the Florida subregion is unique in both its strength and timing, as the highest concentrations consistently occur during the months of April and May. The time series were then deseasonalized and autocorrelations and spectral density estimates calculated, revealing that persistence is much more prevalent in the Florida (autocorrelation significant to a lag of 4 days), south (3 days) and southwest (3 days) subregions. Conversely, autocorrelations are only significant to a lag of one day in the northeast and two days for the Great Lakes and mid-Atlantic subregions.     

南京夏季大气臭氧光化学特征与敏感性分析

对流层臭氧（O₃）主要由氮氧化物（NO_x）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NO_x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.     

Characteristics of ambient volatile organic compounds during spring O3 pollution episode in Chengdu, China

Surface ozone (O₃) has become a critical pollutant impeding air quality improvement in many Chinese megacities. Chengdu is a megacity located in Sichuan Basin in southwest China, where O₃ pollution occurs frequently in both spring and summer. In order to understand the elevated O₃ during spring in Chengdu, we conducted sampling campaign at three sites during O₃ pollution episodes in April. Volatile organic compounds (VOCs) compositions at each site were similar, and oxygenated VOCs (OVOCs) concentrations accounted for the highest proportion (35%-45%), followed by alkanes, alkens (including acetylene), halohydrocarbons, and aromatics. The sensitivity of O₃ to its precursors was analyzed using an observation based box model. The relative incremental reactivity of OVOCs was larger than other precursors, suggesting that they also played the dominant role in O₃ formation. Furthermore, the positive matrix factorization model was used to identify the dominant emission sources and to evaluate their contribution to VOCs in the city. The main sources of VOCs in spring were from combustion (27.75%), industrial manufacturing (24.17%), vehicle exhaust (20.35%), and solvent utilization (18.35%). Discussions on VOCs and NO_x reduction schemes suggested that Chengdu was typical in the VOC-limited regime, and VOC emission reduction would help to prevent and control O₃. The analysis of emission reduction scenarios based on VOCs sources showed that the emission reduction ratio of VOCs to NO₂ needs to reach more than 3 in order to achieve O₃ prevention. Emission reduction from vehicular exhaust source and solvent utilization source may be more effective.     

太湖水体Chl-a预测模型ARIMA的构建及应用优化

叶绿素a（Chl-a）是湖泊浮游植物生物量的重要指标,其含量能反映水中浮游植物的丰度和变化规律.以1999年12月~2019年8月太湖水体Chl-a和环境因子的逐月监测数据为基础,运用主成分分析方法探讨了Chl-a与环境因子的关系,据此建立了Chl-a与主要环境因素之间的多元线性逐步回归模型及自回归综合移动平均模型（ARIMA）.结果表明：①太湖Chl-a浓度存在着明显的季节变化,且总体处于上升趋势.总磷（TP）、高锰酸盐指数、月均气温（MAT）和月度降雨量（MR）与Chl-a浓度存在较好的变化同步性,总氮（TN）和氨氮（NH₄⁺-N）则表现出明显的滞后性.②主成分分析结果表明,太湖水体藻类暴发条件不仅仅是基于N和P等限制性因素,而是发展为TN、NH₄⁺-N、TP和高锰酸盐指数、MR和MAT等多元因素的综合影响.③两种模型经验证比较,基于1999~2019年逐月资料建立的Chl-a浓度的ARIMA模型模拟效果和预测精度明显优于所建立的多元线性逐步回归模型,特别是在考虑主要环境因素作为自变量及优化自变量取值情况下其预测效果得到进一步提升.建立的ARIMA（0,1,1）（0,1,1）模型将有助于太湖藻类暴发的预报和预警,并为及时有效地安排水资源调度及调控等水环境管理措施提供依据.     

Accurate prediction of air quality response to emissions for effective control policy design

Designing effective control policy requires accurate quantification of the relationship between the ambient concentrations of O₃and PM_2.5and the emissions of their precursors.However,the challenge is that precursor reduction does not necessarily lead to decreases in the concentrations of O₃and PM_2.5,which are formed by multiple precursors under complex physical and chemical processes;this calls for the development of advanced model technologies to prov...     

夏季城市大气O3浓度影响因素及其相关关系

利用2003年夏季济南市区近地面大气O₃、相关前体物和气象因素等观测数据,研究了O₃浓度的分布特征及时间变化规律,分析了7月份O₃与NO、NO₂和CO等前体物及太阳辐射和气温气象条件的相关性.结果表明,济南市区夏季O₃污染比较严重,观测期间各污染物O₃、NO、NO₂、NO_x和CO浓度都相对较高,昼间O₃与各前体物的浓度呈较好的负相关关系,与太阳辐射具有非常明显的相关性,而与气温的相关性不明显.根据以上分析结果,利用回归分析方法,建立了昼间O₃浓度与前体物、气象因子之间的相关模式,结果表明O₃浓度的计算值与观测值符合性较好.     

Impact of elevated O3 and CO2 exposure on potato (Solanum tuberosum L. cv. Bintje) tuber macronutrients (N,P, K,Mg, Ca)

It was investigated whether exposure of elevated ozone (O₃) and carbon dioxide (CO₂) concentrations affected the macronutrient (N, P, K, Mg, Ca) concentrations in potato (Solanum tuberosum L.) tubers in three open-top chamber experiments from Sweden and Finland. The tuber concentrations of N, P, K and Mg correlated positively with O₃ exposure (although not significantly in the case of N and P) but the O₃ exposure had no effect on the tuber concentration of Ca. A likely mechanism behind the observed O₃ effects was suggested to be that the more progressed senescence of O₃ exposed plants was associated with a larger extent of reallocation of mobile nutrients from the haulm to the tubers. In addition, the uptake of macronutrients may have been less negatively affected by O₃ exposure than the assimilation of carbon. O₃ tended to reduce the total tuber contents of all investigated nutrients, which imply a reduced fertilizer need per unit field area. This was not associated with a decreased fertilizer need per tonnage of yield, as the tuber nutrient concentrations were increased by O₃ exposure. The increased CO₂ concentration did not significantly affect any of the investigated macronutrients in the present dataset but did generally prevent the O₃ induced increases in nutrient concentrations to be expressed (only significant in the case of N and Mg). The O₃ induced increase in tuber K concentration, may mediate earlier observed O₃ effects on potato tuber concentrations of citric and malic acids. To conclude, anticipated future (and even presently occurring) O₃ exposure has a negative impact on the total tuber contents of K and Ca and probably also on the total tuber contents of N, P and Mg. O₃ exposure causes increased tuber concentrations of N, P, K and Mg at an early harvest. The O₃ induced increase in tuber concentration tended to diminish by a CO₂ elevation.     

泰安市大气臭氧污染特征及敏感性分析

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(O_3)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(NO_x)和VOCs的日变化趋势整体呈现夜间高白天低的变化特征.由O_3生成效率(OPE)、VOCs/NO_x和H_2O_2/NO_z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O_3光化学生成偏向于NO_x敏感区及过渡区,削减NO_x和VOCs均对O_3生成具有控制作用.同时基于EKMA曲线的方法还得出在O_3前体物浓度减排时按照丙烯等效浓度(PE)与NO_x浓度比值为8∶3进行VOCs(PE)和NO_x削减可以达到O_3浓度控制的最佳效果.     

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.     

支持向量机回归在臭氧预报中的应用

采用南京工业区2016年5月20日~8月15日这一高臭氧（O₃）期的O₃、O₃前体物和常规气象资料数据,利用支持向量机回归（SVMr）方法分别预报O₃的小时值、日最大值和最大8 h滑动平均值.结果表明,O₃小时值预报的相关系数（R²）为0.84,平均绝对误差（MAE）和平均绝对百分误差（MAPE）分别为3.44×10^-9和24.48,O₃前期浓度、紫外B波段辐射（UVB）和NO₂浓度是关键因子.O₃日最大值预报的主要因子是NO_x在07：00的浓度和UVB.预报O₃ 8 h时UVB和气温起重要作用.加入前体物项能够使O₃的预报精度提升10%~28%.与多元线性回归方法相比,SVMr对O₃浓度的预报有明显优势.     

Study of tropospheric ozone in the tropical belt (Africa,America) from STRATOZ and TROPOZ campaigns

During three large-scale airborne scientific missions (STRATOZ III: June 1984; STRATOZ III-S: March 1985; TROPOZ I: December 1987), the distributions of ozone and its precursors were measured in the tropical belt over the American and African continents, within an altitude range of 0–12 km. The results reveal an important difference between the northern part of South America, characterized in June by an important O₃ depletion, and West Africa, where high O₃ contents are observed as a result of enhanced formation from bush fires during a large period of the year. O₃ concentrations as high as 160 ppb were observed in the neighborhood of emission areas, corresponding to formation rates on the order of several tens of ppb per hour.     

基于时间序列分解的京津冀区域PM2.5和O3空间分布特征

京津冀区域大气污染分布呈现明显的空间差异,厘清不同时间尺度下PM_2.5和O₃浓度分布有助于制定科学有效的污染防控措施.采用STL方法分解PM_2.5和O₃浓度,获取长期分量、季节分量和短期分量,研究其变化趋势与空间分布特征.结果表明,2017～2021年京津冀区域PM_2.5浓度下降幅度高于O₃,春、夏季PM_2.5和O₃浓度呈正相关,秋、冬季呈现负相关,短期分量和季节分量分别对PM_2.5和O₃浓度的贡献最大. PM_2.5的季节分量、短期分量以及O₃的长期分量和短期分量均存在2个主成分,对应河北省中南部和京津冀区域北部,在不同时间尺度上京津冀区域PM_2.5和O₃均存在次区域分布.与原始序列相比,长期分量能够更好地反映PM_2.5和O₃浓度的演变趋势...     

2020年和2021年南京城区臭氧生成敏感性和VOCs来源变化分析

PM_2.5和臭氧(O₃)协同防控是“十四五”期间空气质量提升的重点.O₃生成与其前体物挥发性有机物(VOCs)和氮氧化物(NO_x)呈高度非线性关系.基于南京市城区站点2020年和2021年的4～9月O₃、 VOCs和NO_x的连续在线监测数据,比较了两年间O₃及其前体物浓度的变化,进一步利用基于观测的盒子模型(OBM)和正定矩阵因子分解(PMF)模型分析了O₃-VOCs-NO_x敏感性和VOCs来源.结果表明,2021年的4～9月O₃日最大浓度、 VOCs和NO_x浓度的平均值相较于2020年同期约下降7%(P=0.031)、 17.6%(P<0.001)和14.0%(P=0.004).2020年和2021年的O₃超标天NO_x和人为源VOCs的平均相对增量反应活性(RIR)分别为0.17和0.14, 0....