Application of positive matrix factorization to identify potential sources of PAHs in soil of Dalian, China

Soil derived sources of polycyclic aromatic hydrocarbons (PAHs) in the region of Dalian, China were investigated using positive matrix factorization (PMF). Three factors were separated based on PMF for the statistical investigation of the datasets both in summer and winter. These factors were dominated by the pattern of single sources or groups of similar sources, showing seasonal and regional variations. The main sources of PAHs in Dalian soil in summer were the emissions from coal combustion average (46%), diesel engine (30%), and gasoline engine (24%). In winter, the main sources were the emissions from coal-fired boiler (72%), traffic average (20%), and gasoline engine (8%). These factors with strong seasonality indicated that coal combustion in winter and traffic exhaust in summer dominated the sources of PAHs in soil. These results suggested that PMF model was a proper approach to identify the sources of PAHs in soil.     

Characterization of particulate polycyclic aromatic hydrocarbons in the east of France urban areas

Background

Air samples collected on three different urban sites in East of France (Strasbourg, Besan?on, and Spicheren), from April 2006 to January 2007, were characterized to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the particulate phase (PM₁₀) and to examine their seasonal variation, diurnal variations, and emission sources.

Results

The average concentrations of ??PAHs were 12.6, 9.5, and 8.9?ng?m^?3 for the Strasbourg, Besan?on, and Spicheren sites, respectively. Strong seasonal variations of individual PAH concentrations were found at the three sampling sites, with higher levels in the winter that gradually decreased to the lowest levels in the summer. The diurnal variations of PAH concentrations in summer presented highest concentrations during the morning (04:00?C10:00) and the evening (16:00?C22:00) times, indicating the important contribution from vehicle emissions, in the three sampling sites. Furthermore, the ratio of BaP/BeP suggests that the photochemical degradation of PAHs can suppress their concentrations in the midday/afternoon (10:00?C16:00), time interval of highest global irradiance. In winter, concentrations of PAH were highest during the evening (16:00?C22:00) time, suggesting that domestic heating can potentially be an important source for particulate PAH, for the three sampling sites.

Conclusion

Diagnostic ratios were used to identify potential sources of PAHs. Results showed that vehicle emissions may be the major source of PAHs, especially in summer, with a prevalent contribution of diesel engines rather than gasoline engines at the three sites studied, independently of the seasons.     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in Pearl River Delta region,China

A level IV fugacity model was applied to simulate the seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in various bulk media in Pearl River Delta (PRD), China. The predictions were validated against monthly observed concentrations of gaseous and particulate phase PAHs in air and annual mean concentrations of all other bulk media. The uncertainty of the predictions was evaluated using Monte Carlo simulation. The influential parameters were identified using sensitivity analysis on both media concentrations and seasonal variations. The predicted concentrations and the patterns of seasonal variation generally agreed with the field observations. Concentrations of gaseous phase PAHs in air increased in the summer and decreased in the winter while concentrations of particulate phase PAHs in summer were lower than those in the winter. The relative variations of PAHs in the other bulk media were not as profound as those in air and the variation patterns were chemical compound dependent. Temperature and precipitation were the most important parameters leading to the seasonalities of PAH concentrations. Other key parameters included dry precipitation rate, advective water flow from upstream, and solid fractions in air and water.     

Seasonal variation and source estimation of organic compounds in urban aerosol of Augsburg, Germany

This study reports a general assessment of the organic composition of the PM_2.5 samples collected in the city of Augsburg, Germany in a summer (August-September 2007) and a winter (February-March 2008) campaign of 36 and 30 days, respectively. The samples were directly submitted to in-situ derivatisation thermal desorption gas chromatography coupled with time of flight mass spectrometry (IDTD-GC-TOFMS) to simultaneously determine the concentrations of many classes of molecular markers, such as n-alkanes, iso- and anteiso-alkanes, polycyclic aromatic hydrocarbons (PAHs), oxidized PAHs, n-alkanoic acids, alcohols, saccharides and others.The PCA analysis of the data identified the contributions of three emission sources, i.e., combustion sources, including fossil fuel emissions and biomass burning, vegetative detritus, and oxidized PAHs. The PM chemical composition shows seasonal trend: winter is characterized by high contribution of petroleum/wood combustion while the vegetative component and atmospheric photochemical reactions are predominant in the hot season.     

Diurnal and seasonal cycles of ozone precursors observed from continuous measurement at an urban site in Taiwan

Hourly measurement of 56 ozone precursors was conducted by a monitoring station located in a metropolitan area in central Taiwan. After nearly a year of continuous operation at this urban site, both diurnal and seasonal cycles of nonmethane hydrocarbons (NMHCs) were clearly observed, which was caused by the interplay between source, chemical loss, and meteorology. Selected species representing three different types of major sources namely the household fuel leakage, vehicular exhaust and gasoline evaporation, as well as biogenic emissions exhibit dramatic diurnal or seasonal cycles with each displaying its own unique characteristics.Ethane and propane, largely originated from leakage of natural gas or liquefied petroleum gases (LPG), showed concentrations elevating throughout the night and early morning, but began to decrease towards noon as the nocturnal temperature inversion elevated. Because of the lower chemical reactivity and somewhat more constant emissions than other measured target compounds, their diurnal cycles were presumably the direct reflection of the mixing height over the metropolitan area.For compounds originating from vehicular plus evaporative emissions such as benzene, which accounts for most of the monitored compounds, their diurnal cycles were also largely controlled by the variation in the height of temperature inversion.Of all the 56 species monitored, isoprene, an abundant biogenic species largely released by plants, showed distinct diurnal and seasonal cycles different from the other measured NMHCs. Its concentration usually peaked at noon in summer and fall when temperature and solar radiation reached their maximum level, demonstrating the close relationship of isoprene with photosynthesis.Seasonal variation was also clearly observed for the other NMHCs quantified. With the exception of isoprene, most species show higher average concentration in winter and lower in summer with the fall values being the intermediate, which presumably is caused by both the seasonal variation in HO abundance and the height of the temperature inversion.     

南京市气溶胶PM2.5中多环芳烃来源识别

对2005年7月至2006年2月采集到的南京市气溶胶Pm2.5 进行季节性初步分析,并对其中的15种优控多环芳烃(PAHs)进行分析研究,通过比值法判断南京市PAHs夏季主要来源于柴油型燃烧,冬季主要来源于柴油和煤型相结合的燃烧.对15种优控PAHs两两之间的相关性分析,发现各化合物之间显著相关,表明各化合物的来源有相似之处.     

Spatio-Temporal Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Atmospheric Air of Tamil Nadu,India, and Human Health Risk Assessment

This study analyzed the seasonal distribution and the possible sources of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric environment of Tamil Nadu, India. Passive air sampling was performed at 32 locations during the period from April 2009 to January 2010, and PAHs were quantified using a gas chromatograph-mass spectrometer. Analysis showed that the concentrations of PAHs were in the range of 5–47.5 ng/m³ with uniform distribution in urban areas in all seasons. Pre-monsoon season showed the highest cumulative concentration of PAHs in both agricultural and coastal areas. Among PAHs, phenanthrene, fluoranthene, and pyrene levels were found to be predominant in all the samples, contributing up to 36%, 35.5%, and 24.5% of total PAHs, respectively. The signature of the PAHs obtained through diagnostic ratio and principal component analysis revealed that diesel emissions was the probable source of PAHs in all locations. Based on Word Health Organization guidelines, the human lung cancer risk due to observed level of PAH concentration (i.e., PAHs exposure) is meager. However, the risk is predicted to be more in the coastal area during summer (18 individuals among 0.1 million people). To the knowledge of these authors, this report is the first on the seasonal analysis of PAHs using passive air sampling in India.     

Estimation and validation of PM2.5/PM10 exhaust and non-exhaust emission factors for practical street pollution modelling

In order to carry out efficient traffic and air quality management, validated models and PM emission estimates are needed. This paper compares current available emission factor estimates for PM₁₀ and PM_2.5 from emission databases and different emission models, and validates these against eight high quality street pollution measurements in Denmark, Sweden, Germany, Finland and Austria.The data sets show large variation of the PM concentration and emission factors with season and with location. Consistently at all roads the PM₁₀ and PM_2.5 emission factors are lower in the summer month than the rest of the year. For example, PM₁₀ emission factors are in average 5–45% lower during the month 6–10 compared to the annual average.The range of observed total emission factors (including non-exhaust emissions) for the different sites during summer conditions are 80–130 mg km⁻¹ for PM₁₀, 30–60 mg km⁻¹ for PM_2.5 and 20–50 mg km⁻¹ for the exhaust emissions.We present two different strategies regarding modelling of PM emissions: (1) For Nordic conditions with strong seasonal variations due to studded tyres and the use of sand/salt as anti-skid treatment a time varying emission model is needed. An empirical model accounting for these Nordic conditions was previously developed in Sweden. (2) For other roads with a less pronounced seasonal variation (e.g. in Denmark, Germany, Austria) methods using a constant emission factor maybe appropriate. Two models are presented here.Further, we apply the different emission models to data sets outside the original countries. For example, we apply the “Swedish” model for two streets without studded tyre usage and the “German” model for Nordic data sets. The “Swedish” empirical model performs best for streets with studded tyre use, but was not able to improve the correlation versus measurements in comparison to using constant emission factors for the Danish side. The “German” method performed well for the streets without clear seasonal variation and reproduces the summer conditions for streets with pronounced seasonal variation. However, the seasonal variation of PM emission factors can be important even for countries not using studded tyres, e.g. in areas with cold weather and snow events using sand and de-icing materials. Here a constant emission factor probably will under-estimate the 90-percentiles and therefore a time varying emission model need to be used or developed for such areas.All emission factor models consistently indicate that a large part (about 50–85% depending on the location) of the total PM₁₀ emissions originates from non-exhaust emissions. This implies that reduction measures for the exhaust part of the vehicle emissions will only have a limited effect on ambient PM₁₀ levels.     

PAHs in the bulk atmospheric deposition of the Seine river basin: source identification and apportionment by ratios, multivariate statistical techniques and scanning electron microscopy

The origin of polycyclic aromatic hydrocarbons (PAH) contamination in bulk atmospheric deposition at two sites of the Seine estuary, one urban and one industrial, has been investigated. The PAH profiles indicate that PAHs mainly have a pyrolytic origin, both in urban and industrial areas. PAH sources vary during the year with an increase of high molecular weight PAH proportions (especially for carcinogenic PAHs) in winter, that means an increase of combustion processes such as domestic heating. Ratios of indicator PAHs (FTH/FTH+PYR and IcdP/IcdP+BghiP) confirm the pyrolytic origin of PAHs. In summer, ratios show the presence of industrial sources. In addition to these two methods, a factor analysis/multiple linear regression model was applied and gave an approximation of PAH source apportionment. PAH were found to be associated predominantly with emissions from road traffic (gasoline and diesel), that accounts for 17-34%. Domestic heating is a very important PAH source in urban areas and accounts for up to 85% of PAHs in winter. Industrial emissions (refineries...) account for 25% in the industrial area in summer. Each is an identified source category for the region and these results are consistent with fly-ashes identified by scanning electron microscopy. This study demonstrates that a combination of source identification methods is a far more efficient than one method alone.     

Tracer-based source apportionment of polycyclic aromatic hydrocarbons in PM2.5 in Guangzhou, southern China, using positive matrix factorization (PMF)

From 28 November to 23 December 2009, 24-h?PM_2.5 samples were collected simultaneously at six sites in Guangzhou. Concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) together with certain molecular tracers for vehicular emissions (i.e., hopanes and elemental carbon), coal combustion (i.e., picene), and biomass burning (i.e., levoglucosan) were determined. Positive matrix factorization (PMF) receptor model combined with tracer data was applied to explore the source contributions to PAHs. Three sources were identified by both inspecting the dominant tracer(s) in each factor and comparing source profiles derived from PMF with determined profiles in Guangzhou or in the Pearl River Delta region. The three sources identified were vehicular emissions (VE), biomass burning (BB), and coal combustion (CC), accounting for 11?±?2 %, 31?±?4 %, and 58?±?4 % of the total PAHs, respectively. CC replaced VE to become the most important source of PAHs in Guangzhou, reflecting the effective control of VE in recent years. The three sources had different contributions to PAHs with different ring sizes, with higher BB contributions (75?±?3 %) to four-ring PAHs such as pyrene and higher CC contributions (57?±?4 %) to six-ring PAHs such as benzo[ghi]perylene. Temporal variations of VE and CC contributions were probably caused by the change of weather conditions, while temporal variations of BB contributions were additionally influenced by the fluctuation of BB emissions. Source contributions also showed some spatial variations, probably due to the source emission variations near the sampling sites.     

The seasonal changes in the concentration of polycyclic aromatic hydrocarbons in precipitation and aerosol near Lake Balaton, Hungary.

The concentration of polycyclic aromatic hydrocarbons (PAHs) in atmospheric precipitation and aerosol samples was monitored in a rural site by Lake Balaton, Hungary to examine the seasonal variation. The seasonal mean concentration of individual 3-6-ring PAHs in precipitation varied from 1 to 54 ng l-1 and from 3 to 350 ng l-1 in summer and winter, respectively. In the atmospheric aerosol samples the seasonal mean concentration of PAHs varied from 4 to 880 pg m-3, from 4 to 300 pg m-3, from 11 to 1050 pg m-3 and from 36 to 5000 pg m-3 in spring, summer, autumn and winter, respectively. Wet (412 micrograms m-2 year-1) and aerosol (190-300 micrograms m2 year-1) deposition rates were also estimated indicating that the two processes are of comparable importance in the removal of 3-6-ring PAHs from the atmosphere.     

Daily, weekly, and seasonal time courses of VOC concentrations in a semi-urban area near Barcelona

In order to study the daily, weekly, and seasonal patterns and possible origins of air concentrations of volatile organic compounds (VOCs), measurements were taken on a minute-by-minute basis with a PTR-MS in the vicinity of a highway in a semi-urban site near Barcelona. Four periods of the year were chosen and samples were taken under different meteorological conditions and at different phenological stages of the surrounding vegetation. None of the measured VOCs concentrations exceeded air-quality guidelines. The results showed that diurnal, weekly, and seasonal fluctuations in measured VOC concentrations depended on variations in the strength of sources, as well as on photochemical activity and meteorological conditions. There was a decrease in concentrations in most VOCs when mixing depth, photochemical destruction, and wind speed increased at midday. On the other hand, high values of some VOCs occurred at night when the strength of their sinks and the mixing layer decreased. Interestingly, in June, night emissions and concentration peaks of methanol and acetone occurred in periods with dew formation and no wind. VOCs related to anthropogenic emissions presented a weekly pattern of variation with a clear distinction being found between working days and the weekend. The seasonal variation showed higher levels in December for all VOCs, except for isoprene. The thinning of the mixing layer leading to greater concentrations of volatiles and lower wind speeds in winter could account for those higher VOC levels. Benzene and toluene originated mainly from anthropogenic emissions. The sources of acetaldehyde, methanol, and acetone appeared to be mainly biogenic and these compounds were the most abundant of all the measured VOCs. Isoprene concentration patterns suggest a predominantly anthropogenic origin in December and March and a mainly biogenic origin in June and October. All these data provide useful information on the dynamics of VOCs in an area where ozone levels in summer exceed quite often the standard protection thresholds for O₃.     

Source Apportionment and Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment Cores of Selected Creeks in Delta State,Nigeria

Polycyclic aromatic hydrocarbons (PAHs) seasonal variation and sources in Ubeji, Ifie, and Egbokodo Creeks of the Niger Delta, Nigeria, were predicted using diagnostic ratios (DRs) of parent PAHs (Phe/Phe + Ant; Flu/Flu + Pyr; BaA/BaA + Chry, and Ind/Ind + BghiP) and principal component analysis (PCA). A total of 222 sediment core samples were collected during the wet (August 2010) and the dry seasons (January 2011). The samples were dried and Soxhlet extracted; sample extracts were fractionated and analyzed by gas chromatography/flame ionization detection (GC/FID) to identify individual PAHs. The diagnostic PAH ratios revealed that PAHs in the sediment cores at the three creeks, in both seasons, mainly stemmed from the combustion process (pyrogenic sources). Principal component analysis further confirmed that wood-burning, coal combustion, diesel, gasoline-powered vehicular emissions, and petroleum combustion were the dominant contributors of PAHs sources at the sampling location. This study provided information on the origin and sources of PAHs in sediment cores, which may be useful for regulatory actions, environmental quality management, contamination history, and environmental forensic studies.     

Sources and seasonal variation of atmospheric polycyclic aromatic hydrocarbons in Dalian,China: Factor analysis with non-negative constraints combined with local source fingerprints

Vapor- and particulate-phase polycyclic aromatic hydrocarbon (PAH) samples were continuously collected at an urban site in Dalian, China, during the heating and non-heating period. There is strong temperature dependence and obvious seasonal trend for atmospheric PAHs, and significant positive correlations of atmospheric PAHs with SO₂ and CO concentrations were observed. Factor analysis model with non-negative constraints (FA–NNC) combined with local and literature PAH source fingerprints was successful in source identification of particulate PAHs in the atmospheric samples. The results suggested that, in heating period, the main pollution sources were identified as coal-fired boiler emission (56%), residential coal combustion (33%) and traffic emissions (11%). As for non-heating period, the main sources were gasoline engine emission, traffic tunnel emission and coal-fired power plant, and the overall source contributions of traffic emission (gasoline engine + traffic tunnel) were 79% and coal-fired power plant 21%. The current results support our previous study and provide new insights. This can be the first attempt to quantitatively apportion air organic pollutants using receptor models combined with local source fingerprints. The source fingerprints can be used as reference data for source apportionment of atmospheric PAHs of China.     

Improved land cover and emission factors for modeling biogenic volatile organic compounds emissions from Hong Kong

This paper describes a study of local biogenic volatile organic compounds (BVOC) emissions from the Hong Kong Special Administrative Region (HKSAR). An improved land cover and emission factor database was developed to estimate Hong Kong emissions using MEGAN, a BVOC emission model developed by Guenther et al. (2006). Field surveys of plant species composition and laboratory measurements of emission factors were combined with other data to improve existing land cover and emission factor data. The BVOC emissions from Hong Kong were calculated for 12 consecutive years from 1995 to 2006. For the year 2006, the total annual BVOC emissions were determined to be 12,400 metric tons or 9.82 × 10⁹ g C (BVOC carbon). Isoprene emission accounts for 72%, monoterpene emissions account for 8%, and other VOCs emissions account for the remaining 20%. As expected, seasonal variation results in a higher emission in the summer and a lower emission in the winter, with emission predominantly in day time. A high emission of isoprene occurs for regions, such as Lowest Forest-NT North, dominated by broadleaf trees. The spatial variation of total BVOC is similar to the isoprene spatial variation due to its high contribution. The year to year variability in emissions due to weather was small over the twelve-year period (?1.4%, 2006 to 1995 trendline), but an increasing trend in the annual variation due to an increase in forest land cover can be observed (+7%, 2006 to 1995 trendline). The results of this study demonstrate the importance of accurate land cover inputs for biogenic emission models and indicate that land cover change should be considered for these models.     

Measurements of nitrogen dioxide concentrations at rural sites in the United Kingdom using diffusion tubes

Nitrogen dioxide concentrations have been measured at rural sites in the United Kingdom and have revealed a marked spatial variation. The annual mean NO2 concentration varies from approximately 1 microg Nm-3 in Northern Ireland to approximately 7 microg Nm-3 in East Anglia. Though the temporal resolution of the diffusion tube method is limited by exposure periods of 2-4 weeks, it was possible to detect a marked seasonal variation in NO2 concentration at all sites, with higher values in the winter than in the summer. This is in contrast to the small seasonal variation previously observed at sites in London. Sulphur dioxide concentrations were measured daily using a bubbler method and, if expressed in terms of mass of sulphur and nitrogen, the SO2 and NO2 annual mean concentrations were similar. This is in contrast to an S/N ratio of greater than 3 in total UK emissions of SO2 and NOx. It seems likely that this difference is due to a combination of the different spatial distributions and heights of emissions of SO2 and NOx, the influence of local sources of NOx, and the smaller S/N ratio in Continental European emissions.     

西安大气气相中的多环芳烃

利用PUF被动采样器于2008年8月—2009年7月采集了西安大气样品,研究了大气气相中多环芳烃（PAHs）的含量和季节分布特征。结果表明,西安大气气相中16种美国EPA优控的PAHs（Σ16PAHs）质量浓度为10.9-489.6 ng/m3（平均为143.4 ng/m3）,四季具有明显的季节差异,依次为夏季（62.5 ng/m3）〈春季（80.1 ng/m3）〈秋季（175.8 ng/m3）〈冬季（255.2 ng/m3）。气相中PAHs主要以3-4环为主,占总量的86.5%-94.1%。利用主成分分析法判断四季气相中PAHs的污染来源类型,主要为燃煤和机动车尾气及生物质燃烧的复合源。     

Biomonitoring seasonal variation of urban air polycyclic aromatic hydrocarbons (PAHs) using Ficus benghalensis leaves

Temporal and seasonal variations of polycyclic aromatic hydrocarbons (PAHs) concentrations in leaves of Ficus benghalensis were investigated in Varanasi city (India). Leaf samples were collected from six sites from urban area of Varanasi and from a control site. PAH extraction was done by sonication in dichloromethane-acetone and quantification by GC-MS. In January total leaf PAHs concentrations at all the urban sites were twice higher as compared to other season's viz. summer and rainy. In contrast, at the control site leaf PAHs concentrations showed lower values than urban sites. The maximum concentrations of total PAHs in winter were due to the medium molecular weight PAHs which increases with respect to both low and high molecular weight PAHs. The temporal variation of medium molecular weight PAHs was similar both at the urban and remote sites. These results support biomonitoring ability of Ficus benghalensis leaves to temporal variations in PAHs contamination.     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

Polycyclic aromatic hydrocarbons in atmospheric particles in the metropolitan area of Porto Alegre,Brazil

The aim of the present study is to identify and quantify the main sources of polycyclic aromatic hydrocarbons (PAHs) associated with aerosols (PM₁₀) collected at three different sampling stations: 8° Distrito, CEASA and Charqueadas. The samples were collected between November 2001 and November 2002, and the concentrations of 16 major PAHs were determined according to EPA. The filters containing particulate matter were extracted with dichloromethane in Soxhlet and the extracts were later analysed in a gaseous chromatograph coupled to a mass spectrometer (GS/MS). The average concentrations of PAHs ranged between 0.04 and 2.30 ng m⁻³. The analysis of principal components was applied to the chemical and meteorological variables in order to facilitate the identification of sources of PAHs emission into the atmospheric particulate. The study identified the following sources of PAHs: vehicular emissions, such as diesel oil, petrol, alcohol, and kerosene; industrial emissions, like lubricating oils; emissions from hospital waste burning, and coal burning at power plants.