Molecular composition of organic aerosols at urban background and road tunnel sites using ultra-high resolution mass spectrometry.

Organic aerosol composition in the urban atmosphere is highly complex and strongly influenced by vehicular emissions which vary according to the make-up of the vehicle fleet. Normalized test measurements do not necessarily reflect real-world emission profiles and road tunnels are therefore ideal locations to characterise realistic traffic particle emissions with minimal interference from other particle sources and from atmospheric aging processes affecting their composition. In the current study, the composition of fine particles (diameter ≤2.5 µm) at an urban background site (Elms Road Observatory Site) and a road tunnel (Queensway) in Birmingham, UK, were analysed with direct infusion, nano-electrospray ionisation ultrahigh resolution mass spectrometry (UHRMS). The overall particle composition at these two sites is compared with an industrial harbour site in Cork, Ireland, with special emphasis on oxidised mono-aromatics, polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatics. Different classification criteria, such as double bond equivalents, aromaticity index and aromaticity equivalent are used and compared to assess the fraction of aromatic components in the approximately one thousand oxidized organic compounds at the different sampling locations.

Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons--a review.

Polycyclic aromatic hydrocarbons (PAHs) are of considerable concern due to their well-recognised toxicity and especially due to the carcinogenic hazard which they present. PAHs are semi-volatile and therefore partition between vapour and condensed phases in the atmosphere and both the vapour and particulate forms undergo chemical reactions. This article briefly reviews the current understanding of vapour-particle partitioning of PAHs and the PAH deposition processes, and in greater detail, their chemical reactions. PAHs are reactive towards a number of atmospheric oxidants, most notably the hydroxyl radical, ozone, the nitrate radical (NO3) and nitrogen dioxide. Rate coefficient data are reviewed for reactions of lower molecular weight PAH vapour with these species as well as for heterogeneous reactions of higher molecular weight compounds. Whereas the data for reactions of the 2-3-ring PAH vapour are quite extensive and generally consistent, such data are mostly lacking for the 4-ring PAHs and the heterogeneous rate data (5 and more rings), which are dependent on the substrate type and reaction conditions, are less comprehensive. The atmospheric reactions of PAH lead to the formation of oxy and nitro derivatives, reviewed here, too. Finally, the capacity of PAHs for long range transport and the results of numerical model studies are described. Research needs are identified.

On-road traffic emissions of polycyclic aromatic hydrocarbons and their oxy- and nitro- derivative compounds measured in road tunnel environments.

Vehicular emissions are a key source of polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAH) and nitrated (NPAH) derivatives, in the urban environment. Road tunnels are a useful environment for the characterisation of on-road vehicular emissions, providing a realistic traffic fleet and a lack of direct sunlight, chemical reactivity and non-traffic sources. In the present investigation the concentrations of selected PAHs, OPAHs and NPAHs have been measured in the Parc des Princes Tunnel in Paris (PdPT, France), and at the Queensway Road Tunnel and an urban background site in Birmingham (QT, U.K). A higher proportion of semi-volatile (3-4 ring) PAH, OPAH and NPAH compounds are associated with the particulate phase compared with samples from the ambient environment. A large (~85%) decline in total PAH concentrations is observed between 1992 and 2012 measurements in QT. This is attributed primarily to the introduction of catalytic converters in the U.K as well as increasingly stringent EU vehicle emissions legislation. In contrast, NPAH concentrations measured in 2012 are similar to those measured in 1996. This observation, in addition to an increased proportion of (Phe+Flt+Pyr) in the observed PAH burden in the tunnel, is attributed to the increased number of diesel passenger vehicles in the U.K during this period. Except for OPAHs, comparable PAH and NPAH concentrations are observed in both investigated tunnels (QT and PdP). Significant differences are shown for specific substances between PAC chemical profiles in relation with the national traffic fleet differences (33% diesel passenger cars in U.K. vs 69% in France and up to 80% taking into account all vehicle categories). The dominating and sole contribution of 1-Nitropyrene observed in the PdPT NPAH profile strengthens the promising use of this compound as a diesel exhaust marker for PM source apportionment studies.