Mobile sources of atmospheric polycyclic aromatic hydrocarbons in a roadway tunnel

Amounts of polycyclic aromatic hydrocarbons (PAHs) and oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in samples collected from the air, from the dust on a guardrail, and from the soils on a tunnel roadway at five sampling sites in a regular roadway tunnel were chemically analyzed in order to determine their sources. Among the 23 PAHs found in the air samples, pyrene was found in the highest concentration (43±7.2 ng/m³), followed by fluoranthene (26±4.3 ng/m³). Among 20 oxy-PAHs found in the air samples, anthraquinone was found in the greatest amount (56±3.9 ng/m³). The average concentration of the major PAHs found in the guardrail dust samples were 6.9±0.77 μg/g for pyrene, 5.5±0.76 μg/g for fluoranthene, and 2.6±0.30 μg/g for phenanthrene. The average concentration of the major oxy-PAHs found in the guardrail dust samples were 9.2±3.5 μg/g for anthraquinone and 1.4±0.50 μg/g for 2-methylanthraquinone. The average concentration of the major PAHs found in the soil samples were 1.1±0.31 μg/g for fluoranthene, 0.92±0.21 μg/g for pyrene, and 0.72±0.16 μg/g for phenanthrene. The average concentration of the major oxy-PAHs found in the soil samples were 1.2±0.88 μg/g for anthraquinone, 0.18±0.04 μg/g for 4-biphenylcarboxaldehyde, and 0.13±0.08 μg/g for 2-methylanthraquinone. The BeP ratios calculated from the results suggest that most PAHs found in the samples collected from the roadway tunnel were from automobile exhaust gases.     

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.     

Efficient screening method for determination of polycyclic aromatic hydrocarbons (PAHs) in airborne particles. Application in real samples of Santiago–Chile metropolitan urban area

A rapid analytical approach for determination of polycyclic aromatic hydrocarbons (PAHs) present in real samples of particulate matter (PM10 filters) was investigated, based on the use of water under sub critical conditions, and the subsequent determination by GC-MS (SIM). The method avoids the use of large volumes of organic solvents as dichloromethane, toluene or other unhealthy liquid organic mixtures which are normally used in time-consuming conventional sample preparation methods. By using leaching times <1 h, the method allows determination of PAHs in the range of ng/m³ (detection limits between 0.05 and 0.2 ng/m³ for 1458 m³ of sampled air) with a precision expressed as RSD between 5.6% and 11.2%. The main idea behind this approach is to raise the temperature and pressure of water inside a miniaturized laboratory-made extraction unit and to decrease its dielectric constant from 80 to nearly 20. This effect allows an increase in the solubility of low polarity hydrocarbons such as PAHs. In this way, an extraction step of a few minutes can be sufficient for a quantitative extraction of airborne particles collected in high volume PM10 samplers. Parameters such as: extraction flow, static or dynamic extraction times and water volume were optimized by using a standard reference material. Technical details are given and a comparison using real samples is made between the conventional Soxhlet extraction method and the proposed approach.The proposed approach can be used as a quantitative method to characterize low molecular PAHs and simultaneously as a screening method for high molecular weight PAHs, because the recoveries are not quantitative for molecular weights over 202. In the specific case of the Santiago metropolitan area, due to the frequent occurrence of particulate matter during high pollution episodes, this approach was applied as an efficient short-time screening method for urban PAHs. Application of this screening method is recommended especially during the winter, when periods of clear detriment of the atmospheric and meteorological conditions occur in the area.     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Study of aluminium distribution and speciation in atmospheric particles of different diameters in Nanjing,China

Aluminium (Al) is one of the trace inorganic metals present in atmospheric particles. Al speciation study is essential to better evaluate the mobility, availability, and persistence of trace Al and Al species in the atmosphere. This paper reports Al distribution and speciation in atmospheric particles with aerodynamic diameters >10.0, 10.0–2.5 and <2.5 μm in the urban area of Nanjing, China. Urban particles were collected with a high-volume sampling system equipped with a cascade impactor, which effectively separates the particulate matter into three size ranges. Particulate Al was fractionated into five different forms (insoluble, oxide, organic, carbonate, and exchangeable species) by the modified five-step Tessier's sequential extraction procedure. The main points are as follows: (1) The average levels of Al in PM_2.5, PM_2.5–10 and PM_>10 are 2.02±0.35, 3.04±0.43 and 6.32±0.76 μg m⁻³, respectively, with PM_2.5, PM_2.5–10 and PM_>10 constituting respectively, 17.8±3.1%, 26.7±3.8% and 55.5±6.7% of suspended particulate matter (SPM) mass (11.38 μg m⁻³). (2) The vertical profile of airborne Al in the above three size fractions has been estimated. A significant increase in airborne Al concentrations was found for PM_2.5, PM_2.5–10 and PM_>10 as the sampling height above the ground increased from 2.5 to 17.5 m; however, there was an obvious decrease in airborne Al concentrations between 17.5 and 40.0 m. The maximum mean of total Al in PM_2.5, PM_2.5–10 and PM_>10 occurred between 12.5 and 20.0 m above the ground. (3) The distribution of Al speciation was studied. It was found that the size distribution of airborne Al species followed the order: insoluble species>oxide species>organic species>carbonate species>exchangeable species.     

Persistence of polycyclic aromatic hydrocarbons in sediments in the deeper area of the Northern Adriatic Sea (Mediterranean Sea)

The Po Valley is the most important agricultural and industrial area of Adriatic basin. In this area there are several rivers which transport polycyclic aromatic hydrocarbons (PAHs) into the sea via suspended particulate matter. This study describes the persistence of PAHs in the deep and coastal sediments of the Northern Adriatic. Different environmental conditions were studied: salinity, temperature, sunlight, sediment particle size and organic matter in sediment. The average conditions in the deep areas of the Northern Adriatic are: salinity higher than 37, temperature lower than 11 °C, darkness and clayey sediments with a high organic matter content. These conditions increase the persistence of the PAHs in the deep area of the Northern Adriatic.     

Distribution characteristics of polycyclic aromatic hydrocarbons with particle size in urban aerosols at the roadside in Ho Chi Minh City,Vietnam

The purpose of this study was to characterize size distributions of atmospheric polycyclic aromatic hydrocarbons (PAHs) with 4–6 rings at the roadside in Ho Chi Minh City, Vietnam. Ten PAHs (fluoranthene, pyrene, triphenylene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) in atmospheric particulate matters (PM) at the roadside were measured in the dry and rainy seasons in 2005 at Ho Chi Minh City, using a low-pressure cascade impactor. The PM were separated into nine fractions by their aerodynamic diameter, i.e. >9.0, 9.0–5.8, 5.8–4.7, 4.7–3.3, 3.3–2.1, 2.1–1.1, 1.1–0.7, 0.7–0.4 and <0.4 μm (a final filter). PAHs were analyzed by high-performance liquid chromatography with fluorescence detection. Total PAHs measured were higher in the rainy season than in the dry season. The mass of coarse particles occupied a higher fraction than that of fine particles in both seasons. Total PAHs were mainly concentrated in particles with aerodynamic diameter smaller than 0.4 μm. The particle size distributions of PAHs investigated were bi-modal with a peak in fine particle mode (<2.1 μm) and another peak in coarse particle mode (>2.1 μm). Generally, 5,6-ring PAHs associated mainly with fine particles and 4-ring PAHs spread out in both fine and coarse particles.     

Long-term atmospheric bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in rural areas of Southern Germany

A novel passive sampling technique using a funnel–adsorber–cartridge device was adopted and validated in the field during a long-term monitoring program on the atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in three rural regions of southern Germany. Apart from seasonal variations, fairly stable annual deposition rates around 200 μg m⁻² yr⁻¹ for the sum of PAHs were obtained. The time-integrating passive samplers showed that spatial variability due to topography was negligible and differences between open-field and forest deposition were within a factor of 2. Based on correlations with ambient temperature, advection was identified as the most important factor that controls the atmospheric deposition of PAHs. Gas-adsorption contributes significantly to the deposition of the semivolatile compounds in forests, but particle deposition seems to be the major pathway for all PAHs.     

Effects of biodiesel on emissions of regulated air pollutants and polycyclic aromatic hydrocarbons under engine durability testing

An 80,000-km durability test was performed on two engines using diesel and biodiesel (methyl ester of waste cooking oil) as fuel in order to examine emissions resulting from the use of biodiesel. The test biodiesel (B20) was blended with 80% diesel and 20% methyl ester derived from waste cooking oil. Emissions of regulated air pollutants, including CO, HC, NO_x, particulate matter (PM) and polycyclic aromatic hydrocarbons (PAHs) were measured at 20,000-km intervals. The identical-model engines were installed on a standard dynamometer equipped with a dilution tunnel used to measure the pollutants. To simulate real-world driving conditions, emission measurements were made in accordance with the United States Environmental Protection Agency (USEPA) FTP transient cycle guidelines. At 0 km of the durability test, HC, CO and PM emission levels were lower for the B20 engine than those for diesel. After running for 20,000 km and longer, they were higher. However, the deterioration coefficients for these regulated air pollutants were not statistically higher than 1.0, implying that the emission factors do not increase significantly after 80,000 km of driving. Total (gaseous+particulate phase) PAH emission levels for both B20 and diesel decreased as the driving mileage accumulated. However, for the engine using B20 fuel, particulate PAH emissions increased as engine mileage increased. The average total PAH emission factors were 1097 and 1437 μg bhp h⁻¹ for B20 and diesel, respectively. For B20, the benzo[a]pyrene equivalence emission factors were 0.77, 0.24, 0.20, 7.48, 5.43 and 14.1 μg bhp h⁻¹ for 2-, 3-, 4-, 5-, 6-ringed and total PAHs. Results show that B20 use can reduce both PAH emission and its corresponding carcinogenic potency.     

Investigations into a novel method for atmospheric polycyclic aromatic hydrocarbon monitoring

A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS, with limits of detection of ～0.3 ng m^?3), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD–GC–MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of ～1 μg m^?3 was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s^?1) and 292 nm excitation.     

Identification,abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China

PM_2.5 aerosols were collected in Nanjing, a typical mega-city in China, during summer and winter 2004 and were characterized for aromatic and cyclic compounds using a GC/MS technique to understand the air pollution problem. They include polycyclic aromatic hydrocarbons (PAHs), hopanes, phthalates and hydroxy-PAHs (OH-PAHs). PAHs, hopanes and OH-PAHs presented higher concentrations in winter (26–178, 3.0–18, and 0.013–0.421 ng m⁻³, respectively) than in summer (12–96, 1.6–11, and 0.029–0.171 ng m⁻³, respectively) due to an enhanced coal burning for house heating and atmospheric inversion layers developed in the cold season. In contrast, phthalates are more abundant in summer (109–368 ng m⁻³, average 230 ng m⁻³) than in winter (33–390 ng m⁻³, average 170 ng m⁻³) due to an enhanced evaporation from plastics during the hot season and the subsequent deposition on the pre-existing particles. Generally, all the identified compounds showed higher concentrations in nighttime than in daytime due to inversion layers and increased emissions from heavy-duty trucks at night. PAHs, hopanes and phthalates in Nanjing aerosols are 5–100 times more abundant than those in Los Angeles, USA, indicating a serious air pollution problem in the city. Concentrations of OH-PAHs are 1–3 orders of magnitude less than their parent PAHs and comparable to those reported from other international cities. Source identification using diagnostic ratios of the organic tracers suggests that PAHs in Nanjing urban area are mainly derived from coal burning, whereas hopanes are more attributable to traffic emissions.     

Global atmospheric emission inventory of polycyclic aromatic hydrocarbons (PAHs) for 2004

The global atmospheric emissions of the 16 polycyclic aromatic hydrocarbons (PAHs) listed as the US EPA priority pollutants were estimated using reported emission activity and emission factor data for the reference year 2004. A database for emission factors was compiled, and their geometric means and frequency distributions applied for emission calculation and uncertainty analysis, respectively. The results for 37 countries were compared with other PAH emission inventories. It was estimated that the total global atmospheric emission of these 16 PAHs in 2004 was 520 giga grams per year (Gg y^?1) with biofuel (56.7%), wildfire (17.0%) and consumer product usage (6.9%) as the major sources, and China (114 Gg y^?1), India (90 Gg y^?1) and United States (32 Gg y^?1) were the top three countries with the highest PAH emissions. The PAH sources in the individual countries varied remarkably. For example, biofuel burning was the dominant PAH source in India, wildfire emissions were the dominant PAH source in Brazil, while consumer products were the major PAH emission source in the United States. In China, in addition to biomass combustion, coke ovens were a significant source of PAHs. Globally, benzo(a)pyrene accounted for 0.05% to 2.08% of the total PAH emission, with developing countries accounting for the higher percentages. The PAH emission density varied dramatically from 0.0013 kg km^?2 y in the Falkland Islands to 360 kg km^?2 y in Singapore with a global mean value of 3.98 kg km^?2 y. The atmospheric emission of PAHs was positively correlated to the country's gross domestic product and negatively correlated with average income. Finally, a linear bivariate regression model was developed to explain the global PAH emission data.     

Atmospheric polycyclic aromatic hydrocarbons observed over the North Pacific Ocean and the Arctic area: Spatial distribution and source identification

During the 2003 Chinese Arctic Research Expedition from the Bohai Sea to the high Arctic (37–80°N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected using a modified high-volume sampler that pulls air through a quartz filter and a polyurethane foam plug (PUF). These filters and PUFs were analyzed for particulate phase and gas phase polycyclic aromatic hydrocarbons (PAHs), respectively, in the North Pacific Ocean and adjacent Arctic region. The ∑PAHs (where ∑=15 compounds) ranged from undetectable level to 4380 pg m⁻³ in the particulate phase and 928–92 600 pg m⁻³ in the gas phase, respectively. A decreasing latitudinal trend was observed for gas-phase PAHs, probably resulting from temperature effects, dilution and decomposition processes; particulate-phase PAHs, however, showed poor latitudinal trends, because the effects of temperature, dilution and photochemistry played different roles in different regions from middle-latitude source areas to the high latitudes. The ratios of PAH isomer pairs, either conservative or sensitive to degradation during long-range transport, were employed to interpret sources and chemical aging of PAHs in ocean air. In this present study the fluoranthene/pyrene and indeno[123-cd]pyrene/benzo[ghi]pyrene isomer pairs, whose ratios are conservative to photo-degradation, implies that biomass or coal burning might be the major sources of PAHs observed over the North Pacific Ocean and the Arctic region in the summer. The isomer ratios of 1,7/(1,7+2,6)-DMP (dimethylphenanthrene) and anthracene/phenanthrene, which are sensitive to aging of air masses, not only imply chemical evolving of PAHs over the North Pacific Ocean were different from those over the Arctic, but reveal that PAHs over the Arctic were mainly related to coal burning, and biomass burning might have a larger contribution to the PAHs over the North pacific ocean.     

Analysis of particulate polycyclic aromatic hydrocarbons by on-line coupled supercritical fluid extraction–liquid chromatography–gas chromatography–mass spectrometry

An on-line supercritical fluid extraction–liquid chromatography–gas chromatography–mass spectrometry (SFE–LC–GC–MS) method was developed for the analysis of the particulate polycyclic aromatic hydrocarbons (PAHs). The limits of detection of the system for the quantification standards were in the range of 0.25–0.57 ng, while the limits of determinations for filter samples varied from 0.02 to 0.04 ng m⁻³ (24 h sampling). The linearity was excellent from 5 to 300 ng (R²>0.967). The analysis could be carried out in a closed system without tedious manual sample pretreatment and with no risk of errors by contamination or loss of the analytes. The results of the SFE–LC–GC–MS method were comparable with those for Soxhlet and shake-flask extractions with GC–MS. The new method was applied to the analysis of PAHs collected by high-volume filter in the Helsinki area to study the seasonal trend of the concentrations. The individual PAH concentrations varied from 0.015 to more than 1 ng m⁻³, while total PAH concentrations varied from 0.81 to 5.68 ng m⁻³. The concentrations were generally higher in winter than in summer. The mass percentage of the total PAHs in total suspended particulates ranged from 2.85×10⁻³% in July to 15.0×10⁻³% in December. Increased emissions in winter, meteorological conditions, and more serious artefacts during the sampling in summer season may explain the concentration profiles.     

Compositional fractionation of polycyclic aromatic hydrocarbons (PAHs) in mosses (Hypnum plumaeformae WILS.) from the northern slope of Nanling Mountains,South China

High mountains may serve both as condenser for vapor phase persistent organic pollutants (POPs) and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs along altitudinal profiles is of interest in understanding the role of high mountains in the atmospheric transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in a selected moss species, Hypnum plumaeformae WILS, from two altitudinal profiles on the northern slope of Nanling mountains in Southern China were analyzed and compared with those in air samples. The total PAH concentration in the mosses was 310–1340 ng g⁻¹ dry weight, with phenanthrene being the most abundant. The distribution patterns of PAHs in the moss samples matched well with those in bulk atmosphere deposition in the adjacent source areas. The PAH distribution pattern in the mosses was a composite of both particle-associated and vapor phase PAHs, with heavy PAHs are susceptible to uptake/retention by mosses than light PAHs. A plot of log (C_moss/C_air) against log K_oa gave a good linear relationship in the log K_ao range of 6.7–10.2. It is suggested that the widely spread moss, H. plumaeformae WILS, can be used as an effective tool in the biomonitoring of atmospheric PAHs pollution in East Asia. The concentrations of most PAHs in the mosses generally declined with increasing altitude. In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation are proposed as the major mechanisms for the compositional fractionation of PAHs along the altitudinal profile.     

PAHs associated with the leaves of Quercus ilex L.: Extraction,GC–MS analysis,distribution and sources: Assessment of air quality in the Palermo (Italy) area

In this study, the leaves of Quercus ilex L. were selected as possible bioaccumulators of polycyclic aromatic hydrocarbons (PAHs). Quercus is an evergreen plant that occurs widely in both urban and rural areas. Several sites (urban roadside, urban, urban park, suburban and rural) in and around Palermo city were investigated.The purpose of this research was to optimize analytical method for quercus leaves, investigate the degree of contamination in the urban area of Palermo by comparing PAH concentration in leaves of quercus from the several sites, establish distribution patterns and relate them to possible sources of PAHs. To this aim, the 16 recommended as priority pollutants by the Environmental Protection Agency (EPA) and perylene were analyzed. PAHs were positively correlated to atmospheric particulate gravimetrically determined on filters aspiring a known volume of air in the various stations.The analyses have been performed by gas chromatography coupled to mass spectrometry (GC–MS) in selected ion monitoring (SIM) mode. The total PAH content in the samples ranged from 92 to 1454 μg kg⁻¹ d.w. The higher amounts of PAHs detected in leaves of quercus from the urban area of Palermo compared with the control site are diagnostic of air contamination, in particular in the zones with heavy traffic. The determination of PAHs in the leaves of quercus allows us, with very simple and fast procedures, to assess the quality of the air over a longer period, since PAHs are accumulated over the whole lifetime of the leaves, irrespective of atmospheric conditions at the moment of sampling.     

Contribution ratio of freely to total dissolved concentrations of polycyclic aromatic hydrocarbons in natural river waters

The bioavailability and ecological risk of hydrophobic organic compounds (HOCs) in aquatic environments largely depends on their freely dissolved concentrations. In this work, the freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) including phenanthrene, pyrene, and chrysene were determined for the Yellow River, Haihe River and Yongding River of China using polyethylene devices (PEDs). The results indicated that the order of ratios of freely to total dissolved concentrations of the three PAHs was phenanthrene (66.8 ± 20.1%) > pyrene (48.8 ± 26.4%) > chrysene (5.5 ± 3.3%) for the three rivers. The ratios were significantly negatively correlated with the log K_ow values of the PAHs. In addition, the ratios were negatively correlated with the suspended sediment (SPS) and dissolved organic carbon (DOC) concentrations in the river water, and the characteristics of the SPS and DOC were also important factors. Simulation experiments showed that the ratio of freely to total dissolved concentrations of pyrene in the aqueous phase decreased with increasing SPS concentration; when the sediment concentration increased from 2 g L^?1 to 10 g L^?1, the ratio decreased from 67.6% to 38.4% for Yellow River sediment and decreased from 50.4% to 33.6% for Haihe River sediment. This was because with increasing SPS concentration, more and more DOC, small particles and colloids (<0.45 μm) would enter the aqueous phase. Because high SPS and DOC concentrations exist in many rivers, their effect on the freely dissolved concentrations of HOCs should be considered when conducting an ecological risk assessment.     

Comprehensive assessment of pine needles as bioindicators of PAHs using multivariate analysis. The importance of temporal trends

The importance of the annual and seasonal trends associated to the polycyclic aromatic hydrocarbons (PAHs) biomonitoring by pine needles are studied with a comprehensive use of univariate and multivariate analysis tools. For this purpose, four pine needle sampling campaigns (winter, spring, summer and autumn 2007) were carried out in 29 sites from Portugal. Needles from Pinus pinaster Ait. and Pinus pinea L. trees were collected from all year-classes available in each tree, corresponding to the different shoots of needles coming out every spring and the results of both species were treated separately. Annual trends of polycyclic aromatic hydrocarbons (PAHs) contamination indicate a general increase from the least to the most exposed year-classes, for all seasons. The mean values for the sum of 16 PAHs ranged from 71 ± 33 ng g⁻¹ (dry weight – dw) for new year (2007) needles in the summer to 514 ± 317 ng g⁻¹ (dw) for 2-year needles (2005) in the spring for P. pinea, and between 90 ± 50 ng g⁻¹ (dw) for new year (2007) needles in the summer and 1212 ± 436 ng g⁻¹ (dw) for 3-year needles (2004) in summer for P. pinaster. The seasonal evolution shows the highest concentrations in the winter, then declining to the lowest levels in the summer and rising again from summer to autumn. Principal component analysis confirmed differences between seasons and needle year-classes, more visible for P. pinea samples. The cooler seasons have more affinity towards the lighter more abundant PAHs, as do the older needles. Differences between both pine species are also evident.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.