Interspecies and interregional comparisons of the chemistry of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska

Comparative biogeochemical studies performed on the same plant species in remote areas enable pinpointing interspecies and interregional differences of chemical composition. This report presents baseline concentrations of PAHs and trace elements in moss species Hylocomium splendens and Pleurozium schreberi from the Holy Cross Mountains (south-central Poland) (HCM) and Wrangell–Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Total PAH concentrations in the mosses of HCM were in the range of 473–2970 μg kg^?1 (dry weight basis; DW), whereas those in the same species of Alaska were 80–3390 μg kg^?1 DW. Nearly all the moss samples displayed the similar ring sequence: 3 > 4 > 5 > 6 for the PAHs. The 3 + 4 ring/total PAH ratios show statistically significant differences between HCM (0.73) and Alaska (0.91). The elevated concentrations of PAHs observed in some sampling locations of the Alaskan parks were linked to local combustion of wood, with a component of vehicle particle- and vapor-phase emissions. In HCM, the principal source of PAH emissions has been linked to residential and industrial combustion of coal and vehicle traffic. In contrast to HCM, the Alaskan mosses were distinctly elevated in most of the trace elements, bearing a signature of the underlying geology. H. splendens and P. schreberi showed diverse bioaccumulative capabilities of PAHs in all three study areas.     

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.     

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.     

Emissions of polycyclic aromatic hydrocarbons (PAHs) from the pyrolysis of scrap tires

This work investigated the PAHs generated in a waste-tire pyrolysis process and the PAHs removal by a wet scrubber (WSB) and a flare. IND, DBA, and BaP were found to dominate in the powders of scrap tires before the pyrolysis. The PAHs in the carbon blacks formed in the pyrolysis were mainly 2-, 3-, 6-, and 7-ring PAHs. Nap was the most predominant water-phase PAH in the WSB effluent. About 40% of the water-phase total-PAHs in the WSB effluent were contributed by nine carcinogenic PAHs. NaP, IND, and COR displayed higher mean gas- and particulate-phase concentrations than the other PAHs in the flare exhaust. The mean removal efficiencies of individual PAHs, total-PAHs, and high carcinogenic BaP+IND+DBA were 39.1–90.4%, 76.2%, and 84.9%, respectively for the WSB. For the flare, the mean removal efficiencies of gaseous, particulate, and combined (gaseous+particulate) total-PAHs were 59.8%, 91.2%, and 66.8%, respectively, whereas the removal efficiencies were 91.0%, 80.1%, and 89.1%, respectively for the total-BaPeq. However, the gaseous BaA displayed a negative mean removal efficiency. The total PAH emission rate and factor estimated for the scrap tire pyrolysis plant were 42.3 g d⁻¹ and 4.00 mg kg-tire⁻¹, respectively.     

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.     

Polycyclic aromatic hydrocarbon emission from straw burning and the influence of combustion parameters

A simulated burning experiment was conducted in a tubular furnace system to examine the emission of polycyclic aromatic hydrocarbons (PAHs) from the burning of rice and bean straw, and the influence of combustion parameters was investigated. Total emission amounts of 16 PAHs (∑PAHs) from the burning of rice and bean straw ranged from 9.29 to 23.6 μg g^?1 and from 3.13 to 49.9 μg g^?1, respectively, which increased with the increase of temperatures from 200 to 700 °C. The contribution of combustion to individual PAH yields was about 80.6–100%, which was generally increased with the increase of burning temperature. Moisture content in straw had a negative effect on PAH formation, especially on PAHs with low molecular weight. ∑PAHs emission amounts decreased by 78.2% for bean straw with a moisture content of 30% in comparison with that for dried straw. In addition, PAH emission amounts increased with the increase of O₂ content in supplied air and then decreased, which showed a maximum emission at O₂ content of 40%. The source fingerprint of PAHs in emission from straw burning was established, which showed that naphthalene accounted for 35.0 ± 7.4% of ∑PAHs. Based on the experimental data, emission amounts of ∑PAHs from the burning of rice and bean straw were estimated to be 320–357 and 32.5–76.0 tons to ambient air per year in China, respectively.     

Large PAHs detected in fine particulate matter emitted from light-duty gasoline vehicles

Emission factors of large PAHs with 6–8 aromatic rings with molecular weights (MW) of 300–374 were measured from 16 light-duty gasoline-powered vehicles (LDGV) and one heavy-duty diesel-powered vehicle (HDDV) operated under realistic driving conditions. LDGVs emitted PAH isomers of MW 302, 326, 350, and 374, while the HDDV did not emit these compounds. This suggests that large PAHs may be useful tracers for the source apportionment of gasoline-powered motor vehicle exhaust in the atmosphere. Emission rates of MW 302, 326, and 350 isomers from LDGVs equipped with three-way catalysts (TWCs) ranged from 2 to 10 (μg L⁻¹ fuel burned), while emissions from LDGVs classified as low emission vehicles (LEVs) were almost a factor of 10 lower. MW 374 PAH isomers were not quantified due to the lack of a quantification-grade standard. The reduced emissions associated with the LEVs are likely attributable to improved vapor recovery during the “cold-start” phase of the Federal Test Procedure (FTP) driving cycle before the catalyst reaches operating temperature. Approximately 2 (μg g⁻¹ PM) of MW 326 and 350 PAH isomer groups were found in the National Institute of Standards and Technology standard reference material (SRM)#1649 (Urban Dust). The pattern of the MW 302, 326, and 350 isomers detected in SRM#1649 qualitatively matched the ratio of these compounds detected in the exhaust of TWC LDGVs suggesting that each gram of Urban Dust SRM contained 5–10 mg of PM originally emitted from gasoline-powered motor vehicles.Large PAHs made up 24% of the total LEV PAH emissions and 39% of the TWC PAH emissions released from gasoline-powered motor vehicles. Recent studies have shown certain large PAH isomers have greater toxicity than benzo[a]pyrene. Even though the specific toxicity measurements on PAHs with MW >302 have yet to be performed, the detection of significant amounts of MW 326 and 350 PAHs in motor vehicle exhaust in the current study suggests that these compounds may pose a significant public health risk.     

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.     

Influence of mature compost amendment on total and bioavailable polycyclic aromatic hydrocarbons in contaminated soils

A laboratory microcosm study was carried out to assess the influence of compost amendment on the degradation and bioavailability of PAHs in contaminated soils. Three soils, contaminated with diesel, coal ash and coal tar, respectively, were amended with two composts made from contrasting feedstock (green waste and predominantly meat waste) at two different rates (250 and 750 t ha^?1) and incubated for 8 months. During this period the treatments were sampled for PAH analysis after 0, 3, 6 and 8 months. Total and bioavailable fractions were obtained by sequential ultrasonic solvent extraction and hydroxypropyl-β-cyclodextrin extraction, respectively, and PAHs were identified and quantified by GC–MS. Bioavailability decrease due to sorption was only observed at the first 3 months in the diesel spiked soil. After 8 months, compost addition resulted in over 90% loss of total PAHs irrespective of soil types. Desorption and degradation contributed to 30% and 70%, respectively, of the PAH loss in the spiked soil, while PAH loss in the other two soils resulted from 40% enhanced desorption and 60% enhanced degradation. Compost type and application rates had little influence on PAH bioavailability, but higher PAH removal was observed at higher initial concentration during the early stage of incubation. The bioavailable fraction of PAH was inversely correlated to the number of benzene rings and the octanol–water partition coefficient. Further degradation was not likely after 8-month although over 30% of the residual PAHs were bioavailable, which highlighted the application of bioavailability concept during remediation activities.     

Long-range transport of polycyclic aromatic hydrocarbons (PAHs) from the eastern Asian continent to Kanazawa,Japan with Asian dust

Aerosol particles were collected for 1 year, starting in April 2003, in rural areas of Kanazawa, Ishikawa, Japan to understand the role of Asian dust as a long-range transporter of polycyclic aromatic hydrocarbons (PAHs). Three sampling intervals were designated in this study, namely: (1) Dust period 1 (March 11–19, 2003); (2) Dust period 2 (March 28, 2003–April 9, 2003); and (3) Dust period 3 (April 9, 2004–April 25, 2004). The Asian dust particles are predominantly in the coarse particle size range (2.1–11 μm). PAH analyses were performed separately on both the coarse and fine (<1.1 μm) particle ranges. Seasonal trends in PAH concentrations for coarse and fine particles showed that the Asian dust particles in Dust period 3 contained significant amounts of less-volatile PAHs such as benzo[a]pyrene (BaP) and benzo[g,h,i]perylene (BghiP). A kinetic model developed in this study shows that almost none of these PAHs would be accumulated on Asian dust particles in the atmosphere, due to their extremely slow adsorption rates. These PAHs would have to originate from PAH-polluted soil particles around industrialized areas. Back trajectory analyses suggest that the Asian dust in Dust period 3 came from loess regions around industrialized areas. This indicates that geologic materials play a significant role in the atmospheric circulation of PAHs.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

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.     

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.     

Polycyclic aromatic hydrocarbons in the urban atmospheric particulate matter in the city of Naples (Italy)

An investigation on PAH in the atmospheric particulate matter of the city of Naples has been carried out. Urban atmospheric particulate matter was sampled in three sampling sites (West, East and central areas of the city), whose characteristics were representative of the prevailing conditions. In each site, 24 h samplings for 7 consecutive days were performed during three sampling campaigns, in 1996–1997. The results were comparable with those reported in literature for similar investigations. Total PAH were in the range 2–130 ng m⁻³, with a seasonal variation (autumn/winter vs. summer) in the range 1.5–4.5. The relative contribution of diesel engines vs. gasoline fuelled engines was evidenced.     

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.     

A novel field measurement method for determining fine particle and gas emissions from residential wood combustion

Emission data from residential wood combustion are usually obtained on test stands in the laboratory but these measurements do not correspond to the operational conditions in the field because of the technological boundary conditions (e.g. testing protocol, environmental and draught conditions). The field measurements take into account the habitual practice of the operators and provide the more reliable results needed for emission inventories. In this study, a workable and compact method for measuring emissions from residential wood combustion in winter conditions was developed. The emissions for fine particle, gaseous and PAH compounds as well as particle composition in real operational conditions were measured from seven different appliances. The measurement technique worked well and was evidently suitable for winter conditions. It was easy and fast to use, and no construction scaffold was needed. The dilution of the sample with the combination of a porous tube diluter and an ejector diluter was well suited to field measurement. The results indicate that the emissions of total volatile organic carbon (TVOC) (17 g kg⁻¹ (of dry wood burned)), carbon monoxide (CO) (120 g kg⁻¹) and fine particle mass (PM₁) (2.7 g kg⁻¹) from the sauna stove were higher than in the other measured appliances. In the masonry heaters, baking oven and stove, the emissions were 2.9–9 g kg⁻¹ TVOC, 28–68 g kg⁻¹ CO and 0.6–1.6 g kg⁻¹ PM₁. The emission of 12 PAHs (PAH₁₂) from the sauna stove was 164 mg kg⁻¹ and consisted mainly of PAHs with four benzene rings in their structure. PAH₁₂ emission from other appliances was, on average, 21 mg kg⁻¹ and was dominated by 2-ring PAHs. These results indicate that despite the non-optimal operational practices in the field, the emissions did not differ markedly from the laboratory measurements.     

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.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.