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Compound class specific radiocarbon analysis (CCSRA) was performed for polycyclic aromatic hydrocarbons (PAHs) associated with airborne particulate matter (APM) with diameter <10 microm (PM10) and <1.1 microm (PM1.1) collected from a residential area of suburban Tokyo, Japan, and seasonal and particle-size radiocarbon variations were investigated. Source diagnostic isomer pair ratios indicated mixed contributions from petroleum combustion and from biomass and coal combustion to the PAHs in APM. The delta14C- PAHs in APM, ranging from -787 to -514 per thousand, indicated dominance of fossil fuel combustion. The delta14C of 5-6 rings (HMW) PAHs were higher than the 3-4 rings (LMW) species in both PM10 and PM1.1 samples. The delta14C of HMW-PAHs indicated greater biomass-burning contributions in summer than in winter and no apparent particle-size variation. Conversely, the delta14C of LMW species showed a greater contribution from fossil sources in summer and in larger particles (PM10). This finding could be tentatively attributed to the recondensation of fossil-PAHs vaporized from petroleum sources. A 14C isotopic mass balance approach estimated that biomass burning contributes 17-45% of the PAH burden in suburban Tokyo, and that the increase in the biomass-PAH accounts for approximately 27% and 22% of winter-time elevation of LMW- and HMW-PAHs, respectively. These are far exceeding what is expected from the emission statistics for CO2 and combusted materials in Japan and emphasizing the importance of biomass-burning as a source of PAHs; which, in turn, demonstrates the utility and the significance of field-based source assessment by using CCSRA for an effective regulation of atmospheric pollution by PAHs.

Abstract: The AMS technique was applied to analyse black carbon (BC), total organic carbon (TOC), and previously reported polycyclic aromatic hydrocarbons (PAHs) in PM10 aerosols from a residential area, suburban Tokyo, to determine natural abundance of radiocarbon (14C), an ideal tracer to distinguish fossil fuel (14C-free) from modern biomass combustion sources of pyrolytic products. The 14C concentrations in BC, isolated using the CTO-375 method, were 42% and 30% pMC (in terms of percent Modern Carbon: pMC) in summer and winter, respectively. The 14C concentrations in BC were also compared with those of compound-class specific 14C content of PAHs previously reported for the same samples: they were 45% and 33% pMC in summer and winter, respectively. The 14C signals of BC were identical to those of high molecular weight (MW⩾226, 5–6 rings) PAHs. The resemblance between 14C signals of BC and PAHs can be referred as a ‘certificate’ for the validity of the BC isolation method employed in this study. Also, it suggests that 14C-BC approach can be a surrogate for PAHs specific 14C analyses to monitor seasonal source variation of combustion-derived pyrolytic products. On the other hand, 14C contents of total organic carbon in 2004 were 61% and 42% pMC in summer and winter, respectively. This is likely attributed to higher contribution of plant activity in summer. [Copyright &y& Elsevier]

This is the first report to reveal the particle-water distribution of nitropolycyclic aromatic hydrocarbons (NPAHs) and to discuss their potential risks and utility as indicators of diesel vehicle exhaust particles (DEP). Time-series samples of runoff were collected from a highway, and NPAHs and polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography-mass spectrometry (GC-MS) to study their dynamic behavior. The concentrations of total NPAHs ranged from 11 to 73 ng/L in particulate phase (>0.7μm) and from 2.3 to 4.9 ng/L in dissolved phase (<0.7 μm). Like their PAH analogs, most(81-97%) NPAHswere associated with particulate matter. The organic carbon-normalized in situ partition coefficients (Koc') of NPAHs observed in runoff events (105.8-6.3 for 2-nitrofluoranthene and 105.8-6.2 for 1-nitropyrene [1-NP]) were more than 1 order of magnitude higherthan those expected from their Kow, indicating great affinity for particulate matter such as soot Concentrations of PAHs and NPAHs adjusted by potency equivalency factors and induction equivalency factors showed that the potential risks of NPAHs were smaller than those of PAHs by a factor of more than a hundred for the particulate phase and more than four forthe dissolved phase. Comparison of concentrations and compositions of NPAHs and PAHs among runoff, DEP, gasoline vehicle exhaust particles, boiler exhaust particles, and aerosols suggested that the ratio of 1-NP to total PAHs (1-NP/PAH) is a useful indicator of DEP for source apportionment of PAHs among traffic- related sources. Source-apportionment of PAHs in the runoff by 1-NP/PAH and methylphenanthrene/phenanthrene ratios suggested that most PAHs in the runoff except the second flush peak were derived from DEP but that other pyrogenic sources contributed to the particles at the second flush and thus to the overall runoff particles. [ABSTRACT FROM AUTHOR]

Abstract: We determined the 14C/12C ratio and concentrations of black carbon (BC) and organic carbon (OC) in airborne particulate matter (APM) with diameter <10μm (PM10) collected in Okinawa, Japan, between March and June 2008. During Asian dust events in March and April, APM and OC concentrations in PM10 aerosols were approximately threefold and twofold higher than those during the non-Asian-dust period in June. “Refractory” BC concentrations (i.e., because of refraction, <100% of BC was likely recovered) were also higher during Asian dust events than during the non-Asian-dust period. The percentages of modern carbon (pMC) in BC and OC were much smaller for PM10 aerosols collected during the Asian dust events (mean=41.5% and 62.3%, respectively) than for those collected in the non-Asian-dust period (mean=67.2% and 93.8%, respectively), indicating a strong influence of fossil-fuel-derived carbon during Asian dust events. One sample showed high OC concentration but relatively low BC concentration, suggesting formation during the long-range transport of biogenic organic compounds. The results suggest that not only fossil-fuel-derived air pollutants but also organic compounds derived from biomass in Asia should be considered to better characterize long-range transported aerosols. [Copyright &y& Elsevier]

Abstract: The levels of PM.25 PAHs at Mt. Halla site, Jeju Island, a background site in Korea were observed between March 1999 and March 2002. A seasonal variation was observed for the particulate PAHs concentrations with high levels during cold season similar to Gosan, a nearby coastal background site, due to the seasonal variations of fossil fuel usage in Asia. The total average concentration of ambient particulate PAHs was 404±579 pg m− 3, about one order lower than the ambient level at Gosan. However, the ratios of the anthropogenic inorganic ion concentrations between Mt. Halla and Gosan were smaller, 1.5 for non sea-salt (nss) sulfate and 2.7 for nitrate. Two possible explanations for these characteristics are (1) two sites measured different air parcels and/or (2) the effect of local emissions were different at two sites. Based on the Bep/BaP ratio result, upper air wind direction data, backward trajectory analysis, and LIDAR measurement data at Gosan, it was found that the degree of the effects of local emissions to the sampling sites be the major reason for the different PAHs levels at two sites though, in some cases, the air parcels arriving at Mt. Halla were different from those arriving at Gosan. For secondary aerosol such as nss sulfate, the lower concentration difference indicates both site are affected by regional transport. It points that the measurement result for directly emitted species such as PAHs at Gosan might be significantly influenced by local emissions. [Copyright &y& Elsevier]