Vertical distribution of volatile organic compounds conducted by tethered balloon in the Beijing-Tianjin-Hebei region of China

Volatile organic compounds (VOCs) as precursors of ozone and secondary organic aerosols can cause adverse effects on the environment and human health. However, knowledge of the VOC vertical profile in the lower troposphere of major Chinese cities is poorly understood. In this study, tethered balloon flights were conducted over the juncture of Beijing-Tianjin-Hebei in China during the winter of 2016. Thirty-six vertical air samples were collected on selected heavy and light pollution days at altitudes of 50-1000 meters above ground level. On average, the concentration of total VOCs (TVOCs) at 50-100 m was 4.9 times higher than at 900-1000 m (46.9 ppbV vs. 8.0 ppbV). TVOC concentrations changed rapidly from altitudes of 50-100 to 401-500 m, with an average decrease of 72%. With further altitude increase, the TVOC concentration gradually decreased. The xylene/benzene ratios of 34/36 air samples were lower than 1.1, and the benzene/toluene ratios of 34/36 samples were higher than 0.4, indicating the occurrence of aged air mass during the sampling period. Alkenes contributed most in terms of both OH loss rate (39%-71%) and ozone formation potential (40%-72%), followed by aromatics (6%-38%). Finally, the main factors affecting the vertical distributions of VOCs were local source emission and negative dispersion conditions on polluted days. These data could advance our scientific understanding of VOC vertical distribution.     

基于DOAS地空观测的典型热带地区臭氧敏感性研究

为实现中国节能减排与产业经济协调发展的目标，本研究选取中国碳排放重要来源之一的能源密集型产业，采用空间全局自相关，标准差椭圆，空间局部自相关以及空间杜宾模型等方法对2007—2016年中国30个省域能源密集型产业格局、碳排放强度时空演变特征进行了分析，在空间溢出视角下对能源密集型产业结构演变的碳排放效应进行了探讨.结果表明：①空间自相关Moran''s I检验表明碳排放强度与能源密集型产业集聚均存在显著的空间正相关.②标准差椭圆表明，能源密集型产业有重心迁移的现象，但迁移效果不明显.③空间杜宾结果显示，能源密集型产业集聚与碳排放强度呈现"N"型曲线关系，能源密集型产业的集聚对碳排放强度的影响存在明显的空间溢出效应，人口数量和外商投资会显著抑制碳排放强度.     

Characteristics of ozone and ozone precursors (VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors(VOCs and NOx) was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface O3 pollution with the characteristics of high average daily mean and maximum concentrations(64.0 and 145.4 ppbV in no-rain days, respectively) and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.5–46.1 and 1.8–6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes(60.0% ± 4.3%), alkenes(21.1% ± 5.5%) and aromatics(18.9% ± 3.9%). Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15–0.27 and 0.42–0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.     

Ground-high altitude joint detection of ozone and nitrogen oxides in urban areas of Beijing

Based on observational data of ozone(O3) and nitrogen oxide(NOx) mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011,the temporal and spatial characteristics of mixing ratios were analyzed.The major findings include:urban O3 mixing ratios are low and NOx mixing ratios are always high near the road in November.Vertical variations of the gases are significantly different in and above the planetary boundary layer.The mixing ratio of O3 is negatively correlated with that of NOx and they are positively correlated with air temperature,which is the main factor directly causing vertical variation of O3 and NOx mixing ratios at 600-2100m altitude.The NOx mixing ratios elevated during the heating period,while the O3 mixing ratios decreased:these phenomena are more significant at high altitudes compared to lower altitudes.During November,air masses in the urban areas of Beijing are brought by northwesterly winds,which transport O3 and NOx at low mixing ratios.Due to Beijing’s natural geographical location,northwest air currents are beneficial to the dilution and dispersion of pollutants,which can result in lower O3 and NOx background values in the Beijing urban area.     

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.     

The ignored emission of volatile organic compounds from iron ore sinter process

Iron ore sintering is a major source of gaseous and particulate pollutants emission in iron smelt plant. The aim of present study is to characterize the volatile organic compounds(VOCs) emission profiles from iron ore sintering process. Both sinter pot test and sinter simulation experiment were conducted and compared. Out results showed that sinter process produced large quantity of VOCs together with NOxand SO_2. VOCs and NO were produced simultaneously in sinter pot test from 3 to 24 min after ignition, flowed by SO_2 production from 15 min to the end of sintering. Total VOCs(TVOC) concentration in sinter flue gas was affected by the coal and coke ratio in sinter raw material. The maximum TVOC concentration was 34.5 ppm when using 100% coal as fuel. Sinter simulation experiments found that the number of VOCs species and their concentrations were found by sinter temperature. The largest VOCs species varieties were obtained at 500 °C. Benzene, toluene,xylene and ethylbenzene were major VOCs in sinter flue gas based on the results from both simulation test and sinter pot. It thus demonstrated that in addition to NO_x, SO_2 and metal oxide particles, sinter flue gas also contained significant amount of VOCs whose environmental impact cannot be ignored. Based on our work, it is timely needed to establish a new VOC emission standard for sinter flue gas and develop advanced techniques to simultaneously eliminate multi-pollutants in iron ore sinter process.     

Vertical distributions of tropospheric SO2 based on MAX-DOAS observations: Investigating the impacts of regional transport at different heights in the boundary layer

Information on the vertical distribution of air pollutants is essential for understanding their spatiotemporal evolution underlying urban atmospheric environment. This paper presents the SO₂ profiles based on ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements from March 2018 to February 2019 in Hefei, East China. SO₂ decrease rapidly with increasing heights in the warm season, while lifted layers were observed in the cold season, indicating accumulation or long-range transport of SO₂ in different seasons might occur at different heights. The diurnal variations of SO₂ were roughly consistent for all four seasons, exhibiting the minimum at noon and higher values in the morning and late afternoon. Lifted layers of SO₂ were observed in the morning for fall and winter, implying the accumulation or transport of SO₂ in the morning mainly occurred at the top of the boundary layer. The bivariate polar plots showed that weighted SO₂ concentrations in the lower altitude were weakly dependent on wind, but in the middle and upper altitudes, higher weighted SO₂ concentrations were observed under conditions of middle-high wind speed. Concentration weighted trajectory (CWT) analysis suggested that potential sources of SO₂ in spring and summer were local and transported mainly occurred in the lower altitude from southern and eastern areas; while in fall and winter, SO₂ concentrations were deeply affected by long-range transport from northwestern and northern polluted regions in the middle and upper altitudes. Our findings provide new insight into the impacts of regional transport at different heights in the boundary layer on SO₂ pollution.     

淹水-落干与季节性温度升高耦合过程对消落带沉积物氮矿化影响

为揭示淹水-落干循环及季节性温度升高耦合过程对三峡支流消落带沉积物氮矿化的影响,根据野外调查,选取三峡支流澎溪河上游和下游两个水文断面,150、160和170 m这3个水位高程的沉积物样品,根据库区水文和气温特征,进行淹水-落干控温培养,分析沉积物氮矿化速率和累积量变化.结果表明与低水位高程相比,高水位高程(170 m)消落带总氮和铵态氮含量相对较低,而硝态氮含量较高.沉积物净氮矿化累积量和矿化速率均表现为落干期高于淹水期,且不同水位高程净氮矿化速率均随时间延长而下降.落干期净氮矿化累积量与沉积物总碳含量和碳氮比显著正相关,而淹水期与之负相关(P0.001).沉积物净氮矿化速率在落干期对温度升高敏感(Q_(10)1),而淹水期低水位高程对温度升高不敏感(Q_(10)1).可见,冬季淹水期温度升高对氮矿化影响较小,氮累积且释放缓慢.夏季落干期温度升高加速了氮矿化过程,增加了二次淹水后无机氮素输入水体和水体富营养化的风险.     

VOC emission caps constrained by air quality targets based on response surface model: A case study in the Pearl River Delta Region, China

Because of the recent growth in ground-level ozone and increased emission of volatile organic compounds (VOCs), VOC emission control has become a major concern in China. In response, emission caps to control VOC have been stipulated in recent policies, but few of them were constrained by the co-control target of PM_2.5 and ozone, and discussed the factor that influence the emission cap formulation. Herein, we proposed a framework for quantification of VOC emission caps constrained by targets for PM_2.5 and ozone via a new response surface modeling (RSM) technique, achieving 50% computational cost savings of the quantification. In the Pearl River Delta (PRD) region, the VOC emission caps constrained by air quality targets varied greatly with the NO_x emission reduction level. If control measures in the surrounding areas of the PRD region were not considered, there could be two feasible strategies for VOC emission caps to meet air quality targets (160 µg/m³ for the maximum 8-hr-average 90th-percentile (MDA8-90%) ozone and 25 µg/m³ for the annual average of PM_2.5): a moderate VOC emission cap with <20% NOx emission reductions or a notable VOC emission cap with >60% NO_x emission reductions. If the ozone concentration target were reduced to 155 µg/m³, deep NO_x emission reductions is the only feasible ozone control measure in PRD. Optimization of seasonal VOC emission caps based on the Monte Carlo simulation could allow us to gain higher ozone benefits or greater VOC emission reductions. If VOC emissions were further reduced in autumn, MDA8-90% ozone could be lowered by 0.3-1.5 µg/m³, equaling the ozone benefits of 10% VOC emission reduction measures. The method for VOC emission cap quantification and optimization proposed in this study could provide scientific guidance for coordinated control of regional PM_2.5 and O₃ pollution in China.     

Inter-comparisons of VOC oxidation mechanisms based on box model: A focus on OH reactivity

Volatile organic compounds (VOCs) oxidation processes play a very important role in atmospheric chemistry, and the chemical reactions are expressed in various manners in chemical mechanisms. To gain an improved understanding of VOCs evolution during oxidation processes and evaluate the discrepancies of VOCs oxidation schemes among different mechanisms, we used the total VOC reactivity as a diagnostic and evaluated tool to explore the differences for six widely used chemical mechanisms. We compared the total VOC reactivity evolution under high-NO_x conditions for several sets of precursors, including n-pentane, toluene, ethene, isoprene and a mixture of 57 Photochemical Assessment Monitoring Stations (PAMS) species in a 0-D photochemical box model. Inter-comparison of total VOC reactivity of individual precursor simulations showed discrepancies to different extent of the oxidation schemes among the studied mechanisms, which are mainly attributed to the different lumping approaches for organic species. The PAMS simulation showed smaller discrepancy than individual precursor cases in terms of total VOC reactivity. SAPRC07 and RACM2 performances are found to better match the MCM for simulation of total VOC reactivity. Evidences suggest that the performance in simulating secondary organic products, OH concentrations and NO_x concentrations are related to the OH reactivity discrepancies among various chemical mechanisms. Information in this study can be used in selection of chemical mechanisms to better model OH reactivity in different environments. The results in this study also provide directions to further improve the ability in modelling total VOC reactivity with the chemical mechanisms.