工业园区和城区VOCs组成及化学活性的空间差异对清远大气臭氧污染分布的影响

工业化与城镇化交替演进使珠三角及其周边地区土地利用类型较为复杂。快速的城市化进程使城市建成区与大量村镇工业园区互相交错。这种变化势必会增加挥发性有机物(VOCs)在组分构成和空间分布上的复杂性,并对臭氧(O₃)污染的时空变化产生影响。为厘清这种排放的空间异质性特征及其对O₃污染分布的影响,分别选取可以代表清远市典型工业园区和城市建成区的站点开展观测研究。结果表明:工业园区和城市建成区VOCs浓度水平和污染特征有较大的空间差异,其中代表村镇工业园区的龙塘站VOCs日均浓度为30.42×10^-9,高于代表城市建成区的技师学院站(17.32×10^-9)。龙塘站二甲苯和甲苯的臭氧生成潜势(OFP)比技师学院站高57.6×10^-9,且该值相当于技师学院站排名前10位物种OFP的总和。气象分析表明:2个站点之间并非彼此的上、下风向,而是共同受到局地气团的影响。源解析结果表明:源排放是造成这种空间异质性的内因,其中交通源对技师学院的贡献更高,而工业相关排放源对龙塘的贡献更高。该研究进一步比较了周边站点O₃时间序列的一致性,并模拟2个站点的O₃生成速率。研究发现O₃在局地范围内变化较小,高VOCs排放的地点对局地O₃有较高的贡献,局地内不同地点的O₃生成过程也存在较大差异。据此,笔者提出O₃污染防控建议:短期内可通过技术手段和观测数据发现O₃污染的重要贡献点,并进行针对性的"散乱污"清理整治和涉VOCs行业综合整治,长期看应科学合理规划城市发展布局和产业布局,预留城市通风廊道,以有效减少O₃污染。     

Case studies on summertime measurements of O3, NO2, and SO2 with a DOAS system in an urban semi-industrial region in Athens, Greece

The objective of this study is to analyze the concentrations of SO₂, NO₂, and O₃ measured by a Differential Optical Absorption Spectroscopy (DOAS) system that was operating at the campus of Technological Education Institute of Piraeus during 2008 and 2009 warm periods (July to September) in relation to the prevailing meteorological conditions. The DOAS system was operating in a particularly polluted area of the West part of Attica basin on a continuous basis, measuring the concentration levels of the main pollutants (O₃, NO₂, and SO₂) as well as aromatic hydrocarbon substances (benzene, toluene, and xylene). According to the analysis, the SO₂ concentration levels at this measuring site are rather high and this may be attributed to the characteristics of this measuring site. Proximity of roadways and local circulation are just some of the factors that can affect the concentration levels of monitoring of pollutant concentrations such as NO₂ and surface ozone. The results provide evidence for the occurrence of an atmospheric phenomenon that produces higher ozone concentrations during weekends despite lower concentrations of ozone precursors. This phenomenon is known as the weekend effect.     

A study of ground-level ozone pollution, ozone precursors and subtropical meteorological conditions in central Taiwan

Hourly concentrations of ozone (O(3)), 55 volatile organic compounds (VOCs, ozone precursors) and nitrogen oxides (NOx) were measured at an upwind urban site, a downwind suburban site, and a rural site in central Taiwan, from January 2003 to December 2006. VOC and NOx mean concentrations showed a gradient from high to low across the urban (56 ppb and 34 ppb), suburban (38 ppb and 27 ppb) and rural sites (25 ppb and 21 ppb) but a reverse gradient in ozone across these sites (24, 27, and 29 ppb, respectively). Although there was about twice the difference in VOC concentrations between the urban and rural sites, nearly 65% ozone formation potential was contributed to by the same 9 VOCs. Seasonal patterns showed peak ozone levels in autumn and minima in summer at the urban site, but minima in winter at the downwind suburban and rural sites. Ozone precursor levels, on the other hand, were lowest in summer and highest in winter. The diurnal pattern showed that ozone levels peaked one hour later at the rural site than at the urban site. The ethylbenzene to m,p-xylene ratio, an indicator of the age of the air mass, increased from 0.4 at the urban site to 0.6 at the suburban site and 0.8 at the rural site during daily peak ozone times. This finding suggests the transport of ozone and precursors from upwind to downwind producing elevated ozone levels in the suburban and rural areas. Ozone episodes occurred mostly in days with a mean midday UV index of 6.5 (1 UV index=100 J m(-2)) and wind speed at 1.3 m s(-1) at all three sites.     

衡水夏季典型时段VOCs污染特征及O3污染过程分析

选取臭氧（O₃）污染高发的7月为夏季典型月，采用自动观测设备，从前体物VOCs的浓度水平及O₃生成潜势（OFP），前体物、气象因素与O₃相关性等多方面研究了衡水市O₃污染影响因素，并剖析了一次典型的O₃污染过程，以期为衡水市夏季O₃污染防治提供科学参考。研究结果表明：衡水市VOCs主要组分浓度占比为烷烃 > 烯烃 > 芳香烃 > 乙炔，主要组分对总OFP的贡献为烯烃 > 芳香烃 > 烷烃 > 乙炔；O₃与前体物VOCs、NO₂存在负相关性，与温度存在正相关性；相对湿度低于48%时，O₃和相对湿度呈负相关性，相对湿度高于48%时，O₃和相对湿度呈正相关性；气团中VOCs化学组成稳定性较低，平均VOCs最大增量反应活性（MIR）较低，为4.855gO₃/gVOCs；衡水市7月2—4日重度污染过程受本地生成和区域传输叠加影响。     

A Multivariate Time Series Approach to Study the Interdependence among O3, NO x , and VOCs in Ambient Urban Atmosphere

A multivariate time series approach vector autoregression (VAR) along with impulse response function and variance decomposition technique has been employed to look into the interrelationship among O₃, NO, NO₂, and volatile organic compounds (VOCs, namely, benzene, ethylbenzene, toluene, and xylene in the present study) using 3 months long continuous time series data of 1 h average concentration of these pollutants at one of the traffic sites in Delhi, India. It is found that the VAR of order 2 (i.e., past two lagged values of 1 h interval) is sufficient to represent the observed time series at the station studied. The impulse response function and variance decomposition analysis indicate that O₃ concentration shows an immediate rise and persists for a longer duration (typically 8–10 h) once the impulse of NO₂, benzene, ethylbenzene, or xylene is given in the ambient environment. However, in case of toluene, the reverse effect has been observed. Since O₃ forms in the troposphere due to photolysis of NO₂, it is not surprising that its impulse triggers O₃ formation in the ambient environment. However, in case of VOCs, this has been attributed to their tendency to show higher inclination toward intermediary reactions leading to the formation of O₃ rather than their (VOCs) reaction with O₃. Among VOCs, only toluene has been observed to show higher inclination toward its reaction with O₃. Apart from this, variance decomposition technique also reveals that the relation of NO with NO₂ is more important than the relation of NO with O₃ creating a conducive atmosphere for O₃ formation in the present scenario. Thus, the multivariate time series approach provides significant insight about the role played by the dominant individual VOCs and NO _x in influencing the O₃ concentration in ambient urban atmosphere whereas a photochemical modeling approach gives an overall view of NO _x and VOCs behavior with respect to O₃ by using the O₃ isopleth technique.     

Heavy and trace metal concentrations in three rockpool shrimp species (Palaemon elegans, Palaemon adspersus and Palaemon serratus) from Tenerife (Canary Islands)

Trace metal concentrations (Fe, Cu, Co, Zn, Ni and V) were investigated in three rockpool shrimp species (Palaemon elegans, Palaemon adspersus and Palaemon serratus) from six littoral sampling sites (polluted and non-polluted) of Tenerife in the Canary Islands (Central Eastern Atlantic), Spain. Sex ratio for all three species has been determined: females predominate over males in all species and significant differences in total length and cephalothorax length was detected between sexes, being females larger than males. By other side, concentrations of trace metals were determined in whole specimens. Higher mean values for every metal were observed in P. adspersus. In males, higher values were observed in P. elegans and P. serratus, whereas in P. adspersus, mean values are higher in females. Finally, mean concentrations of trace metals studied were higher, in general terms, in the two clearly polluted stations: Santa Cruz of Tenerife commercial harbour and its fishery dock dependency.     

Variation of Surface Ozone in the Ambient Air of Auckland, New Zealand

A study has been performed on the characteristics and behavior of surface ozone concentrations at four monitoring sites in Auckland, New Zealand (37 degrees S, 174.8 degrees E) for a four-year period (October 1997-October 2001). One monitoring site (rural) was located upwind of the Auckland urban complex, a second downwind (rural-coastal), and a third within the urban area, while the fourth was an elevated urban-city site located 250 m up the Sky Tower in the central city. In contrast to the high elevation site, the diurnal behaviour of ozone at the three low elevation sites followed a typical solar radiation cycle with high ozone during the day and low nocturnal values. The effect of NO(x) titration was distinct at the urban sites. There was also a seasonal variability in the measured ozone levels with high concentrations in spring and a significant summer minimum. The observed surface ozone concentrations in Auckland were significantly lower than other cities of the world, although a potential for high oxidant formation existed. Observed ozone episodes appear to have been either generated locally or the precursors transported via the prevailing southwest wind. A unique feature of Auckland's air quality is the dilution of polluted city air due to the mixing of east-coast air into the clean west-coast circulation leading to the overall lower average concentrations in summer. A second feature is the potential interaction between sea salt particles and ozone that may provide an additional ozone loss mechanism.     

Heavy metals in the SPM of air in the environment surrounding a ferro-alloy industrial plant in India

Prices for ferro-alloys have hardened due to the closure of plants in developed countries on account of increasingly stringent pollution control legislation, resulting in a higher cost of production. A ferro-alloy industry with a capacity of 80000 MT per annum was selected to study the nature of pollution. Because of the objectionable nature of polluting air in and around the plant it was located in a rural area where there was no other industry. The area was agriculturally active and there was no effective control system for this plant.The quality of ambient air around the plant site is discussed in this paper along with the meteorological conditions. The maximum concentration of suspended particulate matter (SPM) was 768 µg/NM³ downwind of the plant, minimum 184 µg/NM³, and the average was more than 446 µg/NM³. The presence of heavy metals, viz. Fe, Mn, Cr and Pb, was also assessed. The concentration of Fe was 50 µg/NM³ downwind and 10 µg/NM³ upwind. The concentration of other metals followed a similar trend.     

臭氧前体物排放清单相关模型及应用

欧美等国家对于O_3污染的研究开展较早,已建立较成熟的O_3污染生成、扩散及空气质量等模型。文章主要介绍评述了美国环保局推荐使用的计算O_3前体物的相关模型(MOVES、NONROAD、SMOKE、EMFAC和EDMS),从基本原理和功能、污染源类型、研究尺度、所需参数等方面对比分析各模型的特点和适用范围,并综述其国内外研究应用情况;讨论了中国在这些模型的使用方面应该注意的问题,如加强开展模型计算结果验证和基础实验获得本土化的模型参数,以及中国开发的相关模型的优势和适用性等。     

气象要素及前体物对青岛市臭氧浓度变化的影响

在深入探讨2013—2015年青岛市区O_3污染随时间变化特征的基础上,系统分析了不同气象要素对O_3浓度的影响,并研究了前体物对O_3生成的影响及贡献。结果表明:青岛市区O_3第90百分位日最大8 h滑动平均值和超标率均在2014年达到最高值;O_3浓度在5—10月较高,12月至次年1月浓度最低;O_3日变化呈单峰型变化规律,白天浓度高,夜间浓度低。强太阳辐射、高温、相对湿度60%左右、风速4 m/s左右、偏南风等气象条件下易出现高浓度O_3。O_3的生成主要受前体物VOCs控制,且烯烃对O_3生成的贡献远高于烷烃和芳香烃,控制VOCs尤其是烯烃组分的排放可有效降低青岛市区O_3浓度。     

An assessment of air quality in Karachi,Pakistan

An atmospheric pollution survey was carried out at 13 sites in Karachi, Pakistan, simultaneously from 0600 h to 2100 h for 15 consecutive days in May 1990 which also included meteorological measurements. The monitoring sites were included along the prevailing wind patterns in Karachi. Carbon monoxide levels in the ambient air were found to reach 9–10 ppm along the busy urban streets whereas CO₂ level exceeded 370 ppm in these areas. Our survey indicates that NO₂ levels were exceeding U.S. ambient air quality standards. Maxmum NO₂ concentrations were observed (0.3–0.5 ppm) during the daytime from 0600 h to 2100 h. The surface ozone maximum around noon at the inland sites reached the levels of 40 ppb and 50 ppb respectively compared to upwind coastal Sites 1 level of 25 ppb. The Pb concentrations were approximately 3- to 7-fold higher than average, which corresponded well to urban air. Fossil fuel SO₄ (excess) and NO₃ were apportionally based on the assumption that these two anions were present as (NH₄)₂SO₄, and NH₄NO₃ in the aerosols. In the eastern part of the city atmospheric sulphate (SO₄) shows the combustion of coal as its source from the vicinity and downwind of a steel manufacturing plant.     

中国城市臭氧的形成机理及污染影响因素研究进展

中国城市臭氧(O3)污染问题日趋严重.O3主要来源于汽车尾气及工业排放氮氧化合物(NOx)和挥发性有机物(VOCs)光化学反应生成,少部分来自于平流层的向下传输.文章介绍了城市O3形成机理研究情况,概述了中国城市臭氧污染浓度特征及气象因子、气候变化、前体物等影响因素研究进展情况,并对未来研究方向进行了展望.     

An implementation plan for using biological indicators to improve assessment of water quality in Thailand

The present study showed a possibility to use phenotypic and proteomic responses in rice plants as an in vivo biomarker to detect higher concentrations of ambient ozone (O₃). The investigation was done on two cultivars of Indian rice using open top chambers ventilated with charcoal filtered air, ambient air, ambient air with 10 ppb O₃ exposure and ambient air with 20 ppb O₃ exposure at a rural site of Varanasi, India. Results showed that the magnitude of O₃ induced specific type of foliar injury directly depends on the duration and concentration of O₃ exposure. Even the internal protein profile of injured and normal leaf demonstrated a differential expression, which directly indicates towards the molecular basis of plant’s response against O₃.     

Effect of dust load on the leaf attributes of the tree species growing along the roadside

Dust is considered as one of the most widespread air pollutants. The objective of the study was to analyse the effect of dust load (DL) on the leaf attributes of the four tree species planted along the roadside at a low pollution Banaras Hindu University (BHU) campus and a highly polluted industrial area (Chunar, Mirzapur) of India. The studied leaf attributes were: leaf area, specific leaf area (SLA), relative water content (RWC), leaf nitrogen content (LNC), leaf phosphorus content (LPC), chlorophyll content (Chl), maximum stomatal conductance (Gs_max), maximum photosynthetic rate (A _max) and intrinsic water-use efficiency (WUEi). Results showed significant effect of sites and species for DL and the leaf attributes. Average DL across the four tree species was greater at Chunar, whereas, the average values of leaf attributes were greater at the BHU campus. Maximum DL was observed for Tectona grandis at Chunar site and minimum for Syzygium cumini at BHU campus. Across the two sites, maximum value of SLA, Chl and Gs_max were exhibited by S. cumini, whereas, the greatest value of RWC, LNC, LPC, A _max and WUEi were observed in Anthocephalus cadamba. A. cadamba and S. cumini exhibited 28 and 27 times more dust accumulation, respectively, at the most polluted Chunar site as compared to the BHU campus. They also exhibited less reduction in A _max due to dust deposition as compared to the other two species. Therefore, both these species may be promoted for plantation along the roadside of the sites having greater dust deposition.     

嘉善前体物与气象因子对臭氧生成的影响及臭氧潜在源区分析

利用2017年嘉善善西超级站臭氧（O₃）及其前体物（NO_x和VOCs）以及气象因子（温度、湿度、风速）逐小时数据,分析了2017年全年NO_x和O₃的变化特征以及春季（4—5月）、夏季（7—8月）NO_x和气象因子对O₃生成的影响,利用O₃生成潜势（OFP）评估了VOCs大气化学反应活性,并通过潜在源区贡献（PSCF）和浓度权重轨迹（CWT）方法分析了嘉善春、夏季O₃潜在源区贡献特征。研究发现：O₃日变化特征为单峰结构,NO_x为弱双峰结构。O₃浓度在3—9月较高,春、夏季O₃浓度峰值分别出现在15：00和14：00,春、夏季的NO_x、O₃日变化与2017年全年日变化趋势基本一致。NO_x对O₃存在滴定作用,且低湿高温有利于O₃浓度的升高。春、夏季O₃生成潜势贡献均表现为烯烃 > 芳香烃 > 烷烃,由于烯烃光化学活性较高,夏季烯烃浓度升高导致其贡献较春季增长约18.1个百分点,且夏季VOCs平均最大O₃增量反应活性高于春季。PSCF和CWT分析结果表明,嘉善春季的潜在源区主要为本地、西南方向和东南方向,夏季的潜在源区主要为本地、西北方向、西南方向以及东南方向。     

合肥市臭氧及其前体物污染特征及源解析

利用合肥市臭氧和VOCs连续观测数据分析了合肥市臭氧及其前体物污染特征,并使用NAQPMS模型研究了合肥市不同季节臭氧来源情况。结果表明:O₃已经成为影响合肥市环境质量的主要污染因子,O₃高值区主要集中在5—6月和9月。合肥市大气VOCs中烷烃含量最丰富,其次是烯烃、芳香烃和炔烃;主要物种为乙烷、丙烷、乙炔、正戊烷、乙烯、环戊烷、异戊烷、正丁烷、异丁烷和甲苯。合肥市O₃生成主要受VOCs控制,其中,烯烃是合肥市O₃生成贡献最大的关键活性组分,乙烯的OFP贡献率居首位。合肥市不同季节O₃来源差异较大,其中,本地排放是主要来源,夏季占比为50%,其余季节占比为30%~45%,O₃存在跨省长距离输送特征,主导风向的变化是造成合肥市臭氧来源季节性变化的重要因素。     

中原城市群臭氧浓度分布特征及来源

利用2015年臭氧(O_3)自动监测数据和源排放清单,分析了中原城市群O_3浓度的空间、时间分布情况,探讨了中原城市群中城市间O_3的相关性,以及O_3浓度、NOx、VOCs、CO及汽车保有量间的相关性。指出中原城市群是全国更是河南O_3污染的严重地区,O_3浓度年内月度变化呈倒"V"型分布,具有明显的北部城市特征;中原城市群9个城市间除开封外其他8个城市间都呈高度正相关性,相关系数均为0.892~0.991;9个城市机动车保有量及NOx、VOCs和CO等前体物的年排放量与其年均O_3浓度之间存在正相关性。分析认为,NOx、VOCs和CO等前体物的排放是中原城市群O_3浓度偏高的主要影响因素,同时O_3浓度也与日照时间、降雨量、植物源VOCs排放量及相邻城市间污染物的空间输送等因素有着密切的关系。     

Evaluation of air pollution phytotoxicity downwind of a phosphate fertilizer factory in India

The effects of air pollution on plants downwind of a fertilizer factory at Udaipur, India, were studied using three woody perennials. Seedlings of these species including a shrub (Carissa carandas L.), a leguminous avenue tree (Cassia fistula L.) and a fruit tree (Psidium guajava L.) were grown in earthen pots at different study sites receiving varying levels of air pollution input. Changes in plant growth, morphological characteristics, photosynthetic pigment, ascorbic acid, N and S contents and in dry matter allocation were considered in relation to the status of ambient air quality. Observations with these parameters have indicated that the ambient air around the factory contained pollutants at phytotoxic levels. Plant height, basal diameter, conopy area, leaf area and chlorophyll, ascorbic acid and foliar-N concentrations decreased with increasing pollution load. However, foliar-S increased slightly at polluted sites. Air pollution load around the factory have also altered the biomass allocation. Root:shoot ratios increased in C. fistula and P. guajava at polluted sites. In contrast, for C. carandas the above ground parts, where foliage assumed predominance showed precedence over the root growth. This species responded characteristically to air pollution stress by allocating more of its photosynthate towards leaf production and shoot growth.     

Characterizing ozone pollution in a petrochemical industrial area in Beijing,China: a case study using a chemical reaction model

This study selected a petrochemical industrial complex in Beijing, China, to understand the characteristics of surface ozone (O₃) in this industrial area through the on-site measurement campaign during the July–August of 2010 and 2011, and to reveal the response of local O₃ to its precursors’ emissions through the NCAR-Master Mechanism model (NCAR-MM) simulation. Measurement results showed that the O₃ concentration in this industrial area was significantly higher, with the mean daily average of 124.6 μg/m³ and mean daily maximum of 236.8 μg/m³, which are, respectively, 90.9 and 50.6 % higher than those in Beijing urban area. Moreover, the diurnal O₃ peak generally started up early in 11:00–12:00 and usually remained for 5–6 h, greatly different with the normal diurnal pattern of urban O₃. Then, we used NCAR-MM to simulate the average diurnal variation of photochemical O₃ in sunny days of August 2010 in both industrial and urban areas. A good agreement in O₃ diurnal variation pattern and in O₃ relative level was obtained for both areas. For example of O₃ daily maximum, the calculated value in the industrial area was about 51 % higher than in the urban area, while measured value in the industrial area was approximately 60 % higher than in the urban area. Finally, the sensitivity analysis of photochemical O₃ to its precursors was conducted based on a set of VOCs/NOx emissions cases. Simulation results implied that in the industrial area, the response of O₃ to VOCs was negative and to NOx was positive under the current conditions, with the sensitivity coefficients of ?0.16~?0.43 and +0.04~+0.06, respectively. By contrast, the urban area was within the VOCs-limitation regime, where ozone enhancement in response to increasing VOCs emissions and to decreasing NOx emission. So, we think that the VOCs emissions control for this petrochemical industrial complex will increase the potential risk of local ozone pollution aggravation, but will be helpful to inhibit the ozone formation in Beijing urban area through reducing the VOCs transport from the industrial area to the urban area.     

The responses of the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity in sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a polluted site: implications for their use in environmental risk assessment

The present study investigates the response of three hepatic biomarkers in adult sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a wastewater outlet of an oil refinery with fish caged at a pristine site used as controls. The biomarkers that were investigated were the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity. In addition, we have measured the levels of polycyclic aromatic hydrocarbons (PAHs) and selected heavy metals (lead, cadmium, mercury, copper and zinc) in sediment samples at the polluted site. Although the polluted site had high environmental levels of PAHs and heavy metals, there was no difference in hepatic EROD activity and HSI between fish caged at the polluted site and controls. On the other hand, GST activity was significantly lower in fish caged at the polluted site compared to controls. Our results point out that the studied biomarkers have limited use in environmental risk assessment studies, at least when caged adult sea bass is used as the sentinel species and complex toxicant mixtures are involved.