Seasonal variation of particulate polycyclic aromatic hydrocarbons associated with PM10 in Guangzhou, China

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in the urban atmosphere. An investigation on seasonal variation of PAHs in the urban atmosphere of Guangzhou, China was conducted in this study. 112 PM10 (particulate matter with aerodynamic diameter < 10 μm) samples were collected at two sites between June 2002 and June 2003. PAHs were analyzed with GC–MS (gas chromatography–mass spectrometry). The result showed that PAHs exhibit distinct seasonal variation. The seasonal concentration for the ∑PAHs ranged from 8.11 to 106.26 ng m^− 3. The average ∑PAHs measured were highest in winter and lowest in summer. The PAHs distribution patterns were similar within each season at two sites. 5–6 ring PAHs were the abundant compounds, which accounted for 65–90% of ∑PAHs and benzo [b + k] fluoranthene dominated in four seasons. The PAHs concentration and distribution pattern fluctuated greatly in winter for the cold air current. Based on the different temperature in winter, the samples were split into two groups. PM10 and the abundance of the PAHs in winter-1 (temperature, 12–22 °C) were much greater than in winter-2 (temperature, 8–12 °C). In winter-1 benzo [b + k] fluoranthene and Indeno [1, 2, 3] pyrene dominated while chrysene and benzo [b + k] fluoranthene dominated in winter-2. Meteorological conditions such as wind speed and temperature had a strong influence on the seasonal variation. Potential sources of PAHs were identified using the molecular diagnostic ratios between PAHs. Results showed fossil fuel combustion may be the major source of PAHs at the two sites.     

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in urban air of Konya, Turkey

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in urban air samples of Konya, Turkey between August 2006 and May 2007. The concentrations of pollutants in both the gas and particulate phase were separately analysed. The average total (gas + particulate) concentrations of PAHs, PCBs and OCPs were determined as 206 ng m^− 3, 0.106 ng m^− 3, 4.78 ng m^− 3 respectively. All of the investigated target compounds were dominantly found in the gas phase except OCPs. Higher air concentrations of PAHs were found at winter season while the highest concentrations of PCBs were determined in September. The highest OCPs were detected in October and in March. In urban air of Konya, PCB 28 and PCB 52 congeners represent 46% and 35% of total PCBs while Phenanthrene, Fluoranthene, Pyrene accounted for 29%, 13%, 10% of total PAHs. HCH compounds (α + β + γ + δ-HCH), total DDTs (p,p′-DDE, p,p′-DDD, p,p′-DDT), Endosulfan compounds (Endosulfan I, Endosulfan II, Endosulfan sulfate) were dominantly determined as 30%, 21%, 20% of total OCPs respectively. Considering the relation between these compounds with temperature, there was no significant correlation observed. Despite banned/restricted use in Turkey, some OCPs were determined in urban air. These results demonstrated that they are either illegally being used in the course of agricultural activity and gardens in Konya or they are residues of past use in environment. According to these results, it can be suggested that Konya is an actively contributing region to persistent organic pollutants in Turkey.     

Aliphatic alkanes and polycyclic aromatic hydrocarbons in atmospheric PM10 aerosols from Baoji, China: Implications for coal burning

Normal alkanes and PAHs in atmospheric PM₁₀ aerosols collected during 2008 winter and spring in Baoji, a mid-scale inland city of China, were determined on a molecular level. Concentrations of n-alkanes ranged from 232 to 3583 ng/m³ with an average of 1733 ng/m³ in winter and from 124 to 1160 ng/m³ with an average of 449 ng/m³ in spring, while PAHs in the PM₁₀ samples were 594 ± 405 and 128 ± 82 ng/m³ in the two seasons. Molecular compositions showed that CPI (odd/even) values of n-alkanes were close to unity for all the samples especially in winter, and diagnostic ratios of PAHs (e.g., Phe/(Phe + Ant), CPAH/ΣPAHs and IcdP/(IcdP + BghiP)) were found similar to those in coal burning smoke with a strong linear relationship (R² ≥ 0.85) between PAHs and fossil fuel derived n-alkanes, demonstrating that coal burning is the main source of n-alkanes and PAHs in the city, especially in winter due to house heating. Concentrations of the determined compounds in Baoji are much higher than those in Chinese mega-cities, suggesting that air pollution in small cities in the country is more serious and need more attention.     

多环芳烃来源与分布及迁移规律研究概述

概述了多环芳烃的来源,就近年来多环芳烃(PAHs)在大气、土壤、植被和水体沉积物中分布与迁移规律的研究成果进行了综述,并展望了未来PAHs研究方向。     

辽河水中PAHs的污染水平及源解析

在辽河的干支流选择12个例行监测断面,分别于2007年8月和11月采集水样,分析16种US EPA（美国环保署）优控多环芳烃（PAHs）的浓度变化。结果表明：辽河丰水期16种PAHs总量的浓度范围为216—848 ng/L,平均值为430 ng/L,枯水期16种PAHs总量的浓度范围为221—1360 ng/L,平均值为660 ng/L。特征指数表明,辽河水中PAHs主要来源于燃料的高温不完全燃烧,燃烧源为机动车、煤和生物质等。     

Size-resolved aerosol chemical concentrations at rural and urban sites in Central California, USA

Aerosol size distributions were measured with Micro Orifice Uniform Deposit Impactor (MOUDI) cascade impactors at the rural Angiola and urban Fresno Supersites in California's San Joaquin Valley during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) winter campaign from December 15, 2000 to February 3, 2001. PM_2.5 filter samples were collected concurrently at both sites with Sequential Filter Samplers (SFS). MOUDI nitrate (NO₃⁻) concentrations reached 66 μg/m³ on January 6, 2001 during the 1000–1600 PST (GMT-8) period. Pair-wise comparisons between PM_2.5 MOUDI and SFS concentrations revealed high correlations at the Angiola site (r > 0.93) but more variability (r < 0.85) at the Fresno site for NO₃⁻, sulfate (SO₄⁼), and ammonium (NH₄⁺). Correlations were higher at Fresno (r > 0.87) than at Angiola (r < 0.7) for organic carbon (OC), elemental carbon (EC), and total carbon (TC). NO₃⁻ and SO₄⁼ size distributions in Fresno were multi-modal and wider than the uni-modal distributions observed at Angiola. Geometric mean diameters (GMD) were smaller for OC and EC than for NO₃⁻ and SO₄⁼ at both sites. OC and EC were more concentrated on the lowest MOUDI stage (0.056 µm) at Angiola than at Fresno. The NO₃⁻ GMD increased from 0.97 to 1.02 µm as the NO₃⁻ concentration at Angiola increased from 43 to 66 µg m^− 3 during a PM_2.5 episode from January 4–7, 2001. There was a direct relationship between GMD and NO₃⁻ and SO₄⁼ concentrations at Angiola but no such relationships for OC or EC. This demonstrates that secondary aerosol formation increases both concentration and particle size for the rural California environment.     

Polycyclic aromatic hydrocarbons (PAHs) associated with atmospheric particles in Higashi Hiroshima, Japan: Influence of meteorological conditions and seasonal variations

This work studied the influence of meteorological conditions on particulate polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Higashi Hiroshima, Japan. The seasonal variation of particulate PAHs was also covered. It was found that ambient temperature, solar intensity and weekly rainfall had significant influence on the particulate PAH concentration based on correlation studies. Correlation of particulate PAHs with ambient temperature, solar intensity, weekly rainfall, wind speed and humidity was studied by using Pearson correlation analysis. Particulate PAHs had a strong negative correlation with ambient temperature and solar intensity. A moderate negative correlation with weekly rainfall was also observed. There was no significant correlation between particulate PAHs with wind speed as well as humidity. Besides, particulate PAHs were found to have significant positive correlation with sulfur dioxide and nitrogen dioxide while having a moderate negative correlation with ozone. The particulate PAHs in Higashi Hiroshima exerted distinct seasonal variation with a higher concentration in winter and lower concentration in summer. When compared among PAHs with different numbers of aromatic rings; 5-ring PAHs was found to exert the most distinct seasonal variation. The contribution of carcinogenic PAHs to total particulate PAH concentration was fairly constant at about 50% throughout the year.     

A summer and winter apportionment of particulate matter at urban and rural areas in northern France

The apportionment of atmospheric aerosols undertaken in Northern France during two sampling campaigns allowed to determine the influence of the atmospheric contribution of a heavy industrialized urban center on the particulate matter composition at a nearby rural site. The concentrations of major components and trace elements sampled by bulk filtration have been determined on June–July 2000 and January–February 2001, and the comparison of these two campaigns shows very well the importance of wind directions. The sources of 10 trace elements (Al, Ba, Cu, Fe, K, Mn, Pb, Sr, Ti and Zn) and 7 major components (Cl⁻, NO₃⁻, SO₄²⁻, NH₄⁺, Na, Mg and Ca) are better identified by studying their elemental contribution at each sampling site according to wind sectors. This kind of study shows that the concentrations recorded at the urban sampling site are always higher than those observed at the rural site as well during the summer campaign (about + 35%) as during the winter campaign (+ 90%), because of the predominance of the W–NW wind sector, corresponding to the influence of the urban and industrialized areas.     

Distribution and source apportionment of Polycyclic aromatic hydrocarbons from atmospheric particulate matter PM<Subscript>2.5</Subscript> in Beijing

A total of 11 PM2.5 samples were collected from October 2003 to October 2004 at 8 sampling sites in Beijing city. The PM2.5 concentrations are all above the PM2.5 pollution standard （65 μg m^-3） established by Environmental Protection Agency, USA （USEPA） in 1997 except for the Ming Tombs site. PM2.5 concentrations in winter are much higher than in summer. The 16 Polycyclic aromatic hydrocarbons （PAHs） listed as priority pollutants by USEPA in PM2.5 were completely identified and quantified by high performance liquid chromatography （HPLC） with variable wavelength detector （VWD） and fluorescence detector （FLD） employed. The PM2.5 concentrations indicate that the pollution situation is still serious in Beijing. The sum of 16 PAHs concentrations ranged from 22.17 to 5366 ng m^-3. The concentrations of the heavier molecular weight PAHs have a different pollution trend from the lower PAHs. Seasonal variations were mainly attributed to the difference in coal combustion emission and meteorological conditions. The source apportionment analysis suggests that PAHs from PM2.5 in Beijing city mainly come from coal combustion and vehicle exhaust emission. New measures about restricting coal combustion and vehicle exhaust must be established as soon as possible to improve the air pollution situation in Beijing city.     

Carbonaceous materials in size-segregated atmospheric aerosols from urban and coastal-rural areas at the Western European Coast

A high-volume cascade impactor, equipped with a PM10 inlet, was used to collect size-segregated aerosol samples during the summer of 2004 at two Portuguese locations: a coastal-rural area (Moitinhos) and an urban area (Oporto). Concentrations of airborne particulate matter (PM), total carbon (TC), organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were determined for the following particle size ranges: < 0.49, 0.49–0.95, 0.95–3.0, and 3.0–10 µm. The total PM mass concentrations at the urban and coastal-rural sites ranged from 22.8 to 79.6 μg m^− 3 and 19.9 to 28.2 μg m^− 3, respectively, and more than 56% of the total aerosol mass was found in the fractions below 3.0 μm. At both locations the highest concentrations of OC and EC were found in the submicrometer size range. The regional variability for the OC and EC concentrations, with the highest concentrations being found in the urban area, was related to the contribution of local primary sources (mostly traffic emissions). It was also verified an enrichment of the small size particles in WSOC, representing on average 37.3(± 12.4)% and 59.7(± 18.0)% of OC in the very fine aerosol at the coastal-rural and urban areas, respectively. The amount of secondary OC calculated by the minimum OC/EC ratio method indicates that secondary organic aerosol formation was important throughout the study at both sites. The obtained results suggest that long-range transport and favourable summer conditions for photochemical oxidation are key factors determining secondary OC formation in the coastal-rural and urban areas. The ultraviolet absorption properties of the chromophoric constituents of the WSOC fractions were also different among the different particle size ranges and also between the two sampling locations, thus suggesting the strong impact of the diverse emission sources into the composition of the size-segregated organic aerosol.     

大气气溶胶粒径分布特征与气象条件的相关性分析

通过温度、相对湿度和风速等气象因素与不同粒径大气气溶胶粒子数浓度和质量浓度的相关性,分析气象条件对大气气溶胶的影响和作用机制。结果表明：气象因素对0.2—0.6 μm的气溶胶影响最大。温度升高既有利于增强大气扩散作用也有利于二次气溶胶生成,因此温度与超细气溶胶(小于0.1μm)呈正相关性,而与粒径较大的气溶胶呈负相关。风速主要影响气溶胶的水平扩散,对超细气溶胶无显著影响,而与粗粒径气溶胶呈负相关。相对湿度会促进超细气溶胶的聚积,使之生成较大粒径气溶胶。因此相对湿度与超细气溶胶呈较强的负相关,而与较粗粒径气溶胶呈正相关。     

On the distribution of physical and chemical particle properties in the atmospheric aerosol

Consideration of sources and growth dynamics of aerosols has led to the conclusion that there may be a distribution or variation of chemical composition and physical structure among atmospheric aerosol particles as a function of size, and within a narrow size range as well. A mathematical representation of these particle properties in terms of an additional dimension to the number size distribution is described. Examples of the relevance of this aspect of aerosol characterization for physical and chemical processes in the atmosphere are discussed. A review of the available techniques shows that several methods are available which can and have provided quantitative results on the distribution of particle properties. Examples of data from the literature have been selected and are presented as three-dimensional distributions illustrating the wide range of particle properties which may exist in narrow size intervals. An evaluation of these results reiterates the value of taking the distribution of particle properties in the atmosphere into account for sampling and modeling purposes.     

Formation and chemical composition of atmospheric aerosols in an equatorial forest area

The physical properties and the chemical composition of atmospheric aerosols have been studied in an equatorial region in the southern Congo (Africa). Field experiments were conducted between 1978 and 1983 in the equatorial forest of the Mayombe during periods where the influence of biomass burning was minimum. The results indicate that the forest is a net source of both fine particles resulting primarily from gas-to-particle conversion and coarse particles produced by mechanical processes. Carbonaceous matter is the major component of these biogenic particles but the forest is also a significant source of sulfate, nitrate, ammonium and potassium. Half of this carbon is attached to submicron particles and likely derives from organic gaseous precursors naturally emitted by the local biosphere.Presented at the international Symposium Influence of marine and terrestrial biosphere on the chemical composition of the atmosphere, held in Mainz, F.R.G., on 16–22 March 1986.     

Determination of selected atmospheric aromatic hydrocarbons at remote continental and oceanic locations using photoionization/flame-ionization detection

A new gas chromatographic technique with a modified photoionization detector connected in series with a conventional flame ionization detector was used to determine low concentrations of atmospheric hydrocarbons in remote atmospheres. Average mixing ratios of five aromatic hydrocarbons measured between 42°N and 30°S latitude in the Pacific Ocean in October/November 1983 were highest in the Northern Hemisphere. The average mixing ratios in the northern and southern marine atmospheres were 49±25 ppt (n=35) and 10±2 ppt (n=21) for benzene, 20±12 ppt (n=32) and 5.6±1.6 ppt (n=12) for toluene, 7.6±3.7 ppt (n=35) and 3.7±1.6 ppt (n=21) for ethylbenzene, 25±12 ppt (n=35) and 13±5 ppt (n=20) for the sum of m- and p-xylenes, and 14±6 ppt (n=35) and 6.6±3.0 ppt (n=21) for o-xylene, respectively. The first latitudinal gradients for these five aromatic compounds are reported. Benzene and toluene mixing ratios measured between July 1982 and October 1983 at a rural, mid-latitude continental site in eastern Washington state gave average values of 226±108 ppt and 133±84 ppt, respectively, with higher wintertime than summertime benzene levels. These continental samples gave calculated air mass ages averaging six days based on benzene-to-toluene ratios.     

北方涛动同北半球温带大气环流的遥相关(二)——季节变化

在以前工作的基础上,本文进一步分析了各个季节北方涛动和与其相联系的北太平洋海温同北半球温带大气环流遥相关的特征,并与南方涛动和赤道太平洋海温的结果进行了比较,发现它们同北半球温带大气环流的遥相关,不仅具有很强的地区性,而且具有明显的季节变化。 冬季,北方涛动和北太平洋海温与PNA型相关非常明显,且比南方涛动和赤道太平洋海温的更密切。除PNA型外,北方涛动还同500hPa高度的亚洲-北美(ANA)流型有联系。 夏季,PNA遥相关型的表现仍然非常清楚,但位置较冬季偏酉和偏北,并在北美西海岸具有特殊的分叉现象。     

青藏高原两类对流层顶频率的季节分布特征及其与同纬度地区的差异

基于1979~2014年ERA-Interim逐日再分析温度资料,依据温度递减率插值法,计算出北半球两类对流层顶(热带对流层顶和极地对流层顶)频率数据。对比分析了青藏高原与同纬度地区两类对流层顶频率在季节变化上的差异,并讨论了青藏高原两类对流层顶频率分布与高空温度的关系。结果表明:1)依据温度递减率插值法计算出的再分析两类对流层顶频率可以反映青藏高原两类对流层顶频率季节变化特征:热带对流层顶全年频率高,冷、暖季节差异不明显;极地对流层顶盛夏频率极低,冷、暖季节差异明显。与极地对流层顶频率相比,青藏高原热带对流层顶频率的可信度更高。2)青藏高原和同纬度地区热带(极地)对流层顶频率在暖季增加(减少),在冷季减少(增加)。相比同纬度地区,青藏高原热带(极地)对流层顶频率在冬季偏少(多),其他季节偏多(少)。青藏高原两类对流层顶频率等值线的梯度更大,表明青藏高原对流层顶更易断裂。3)青藏高原两类对流层顶频率与高空温度关系密切。青藏高原对流层中上层(平流层下部)温度升高(降低),有利于青藏高原热带对流层顶频率增加,极地对流层顶频率减少,反之亦然。     

Using Föhn conditions to characterize urban and regional sources of particles

Characterizations of urban and regional sources of particulate matter (PM) were performed in the Milan area (North of Italy) during Föhn and stagnant (non-Föhn) conditions. The measurements were performed at two different places: in an urban area North of Milan (Bresso) and in a regional area at the EMEP-GAW station in Ispra (about 65 km NW from Milan) during the winter periods of the years 2002–2007. Particle size distributions and chemical bulk analysis of aerosols are combined with single particle mass spectrometry to obtain information about the chemical content of the particles and their mixing state. Föhn conditions are characterized by extremely clean background air from which background aerosol is scavenged, and consequently local sources (here defined as sources between the sampling sites and the mountain range top about 100–150 km away depending on the wind direction) determine the aerosol properties.It was observed that during Föhn events the accumulation mode in the size range 50 nm < d < 300 nm practically disappears and that the size fraction below 50 nm dominates the total number distribution. The significant change in the number size distribution and the large decrease in PM10 mass during Föhn events are accompanied by a significant change in the chemical composition of the particles. Results from bulk chemical analysis showed high amounts of carbonaceous compounds and very low concentrations of ammonium nitrate (as indicator for secondary chemistry) during Föhn episodes, in contrast to stagnant conditions, when secondary components are dominating the aerosol composition. Single particle measurements confirm the high contribution of carbonaceous compounds in locally emitted particles.It was concluded that particles that originated in the urban area come mainly from combustion processes, especially direct traffic emissions, domestic heating and industrial activities, whereas the regionally emitted particles are different with much less traffic contribution.We estimate that under prevailing (non-Föhn) winter conditions, about 50–65% of the aerosol mass load in the city of Milan are caused by local emissions, and about 35–50% come from regional background. This finding suggests that in order to improve air quality in a big city like Milan, it is important to combine local traffic restriction interventions with other long-term regional scale air-quality-measures.     

The differences of the size distribution of polycyclic aromatic hydrocarbons (PAHs) between urban and rural sites of Guangzhou, China

Size distribution aerosol samples collected at two urban locations (Liwan and Wushan) and a suburban location (Xinken) in Guangzhou (South China) in autumn using a MOUDI (Micro-orifice Uniform Deposit Impactor) have been analyzed for 13 polycyclic aromatic hydrocarbons (PAHs) by gas chromatography with mass selective detection (GC-MS). Different PAH size distribution models were found for urban locations and a suburban location. The particle size distributions of PAHs tend to shift toward a larger size in a suburban location than in an urban location caused by aerosol aging processes. The ratios of total-PAH/TSP changed greatly during different sampling periods, even though the samplings were conducted consecutively. This can be the result of reactions between PAHs and atmospheric photooxidants, and the formation of SOAs (secondary organic aerosols) during the aging process. Adsorption behavior on available aerosol surface area, absorption behavior in available aerosol organic mass and multilayer adsorptive accumulation in coarse mode aerosols were the three mechanisms which control the size distribution of PAHs.     

夏季长三角城市群热岛效应及其对大气边界层结构影响的数值模拟

利用WRF/Noah/UCM模拟系统对长三角地区城市群进行了2003—2007年共5个夏季的高分辨率数值模拟,研究了夏季长三角城市群热岛效应及其对大气边界层影响。开展了2组平行的积分试验,控制试验为MODIS遥感资料给出的地表特征分布,敏感性试验将长三角地区的城市表面改为农田类型,其他与控制试验完全相同。两组试验的对比分析表明城市群热岛存在明显的日变化特征,热岛效应白天向上发展较高,夜间地表热岛强度明显增强。城市热岛导致午后城市上空产生强烈的局地上升气流,从而使得低层大气以补偿流的形式向城市辐合,然而在夜间上升运动很微弱。伴随这种热力状况的日变化,大气边界层高度也存在明显的日变化,白天增高,夜间降低。同时,白天城市边界层内风速明显减小,夜间地面风速减小加剧,但夜间边界层顶风速却有所增强。另外,城市化还会导致“城市干岛”现象,且其白天强度大于夜间。     

Simulated Spatial Distribution and Seasonal Variation of Atmospheric Methane over China: Contributions from Key Sources简

We used the global atmospheric chemical transport model,GEOS-Chem,to simulate the spatial distribution and seasonal variation of surface-layer methane （CH4） in 2004,and quantify the impacts of individual domestic sources and foreign transport on CH4 concentrations over China.Simulated surface-layer CH4 concentrations over China exhibit maximum concentrations in summer and minimum concentrations in spring.The annual mean CH4 concentrations range from 1800 ppb over western China to 2300 ppb over the more populated eastern China.Foreign emissions were found to have large impacts on CH4 concentrations over China,contributing to about 85％ of the CH4 concentrations over western China and about 80％ of those over eastern China.The tagged simulation results showed that coal mining,livestock,and waste are the dominant domestic contributors to CH4 concentrations over China,accounting for 36％,18％,and 16％,respectively,of the annual and national mean increase in CH4 concentration from all domestic emissions.Emissions from rice cultivation were found to make the largest contributions to CH4 concentrations over China in the summer,which is the key factor that leads to the maximum seasonal mean CH4 concentrations in summer.