NPAHs and OPAHs in the atmosphere of two central European cities: Seasonality, urban-to-background gradients, cancer risks and gas-to-particle partitioning.

Derivatives of polycyclic aromatic hydrocarbons (PAHs) such as nitrated- and oxygenated-PAHs (NPAHs and OPAHs) could be even more toxic and harmful for the environment and humans than PAHs. We assessed the spatial and seasonal variations of NPAHs and OPAHs atmospheric levels, their cancer risks and their gas-to-particle partitioning. To this end, about 250 samples of fine particulate matter (PM2.5) and 50 gaseous samples were collected in 2017 in central Europe in the cities of Brno and Ljubljana (two traffic and two urban background sites) as well as one rural site. The average particulate concentrations were ranging from below limit of quantification to 593 pg m-3 for Σ9NPAHs and from 1.64 to 4330 pg m-3 for Σ11OPAHs, with significantly higher concentrations in winter compared to summer. In winter, the particulate levels of NPAHs and OPAHs were higher at the traffic site compared to the urban background site in Brno while the opposite was found in Ljubljana. NPAHs and OPAHs particulate levels were influenced by the meteorological parameters and co-varied with several air pollutants. The significance of secondary formation on the occurrence of some NPAHs and OPAHs is indicated. In winter, 27-47% of samples collected at all sites were above the acceptable lifetime carcinogenic risk. The gas-particle partitioning of NPAHs and OPAHs was influenced by their physico-chemical properties, the season and the site-specific aerosol composition. Three NPAHs and five OPAHs had higher particulate mass fractions at the traffic site, suggesting they could be primarily emitted as particles from vehicle traffic and subsequently partitioning to the gas phase along air transport. This study underlines the importance of inclusion of the gas phase in addition to the particulate phase when assessing the atmospheric fate of polycyclic aromatic compounds and also when assessing the related health risk.

Indoor and Outdoor PM10-Bound PAHs in an Urban Environment. Similarity of Mixtures and Source Attribution.

Given that the European Union lays down air quality objectives associated with outdoor environments, indoor air mixtures' study acquires a remarkable relevance. This work aims to submit a stepwise methodological framework for assessing similarities between indoor and outdoor air mixtures and apportioning potential emission sources. For reaching this goal, PM10 particles were systematically and simultaneously collected at an indoor (dominant emission sources free) and outdoor environment during a year to determine the PAH content in both air mixtures. Broadly, outdoor PAHs levels were higher than at the indoor location, supporting a strong association between both mixtures (r = 0.968, p > 0.001), mainly during the cold period (r = 0.896, p > 0.001). The light molecular weight PAHs were highlighted at the indoor site, in particular to naphthalene and anthracene. Outdoor emission sources influenced the indoor PAH levels, especially high and medium molecular weight PAHs. The local-traffic load was identified as a dominant pollution source responsible for more than half PAHs determined at both environments. Therefore, the control of outdoor emission sources would be translated into an improvement of indoor air quality.

Chemical tracers of particulate emissions from commercial shipping.

Despite the increase of commercial shipping around the world, data are yet relatively scarce on the contribution of these emissions to ambient air particulates. One of the reasons is the complexity in the detection and estimation of shipping contributions to ambient particulates in harbor and urban environments, given the similarity with tracers of other combustion sources. This study aimed to identify specific tracers of shipping emissions in a Mediterranean city with an important harbor (Melilla, Spain). Results showed that for 24 h PM10 and PM2.5 samples, valid tracers of commercial shipping emissions were ratios of V/Ni = 4-5 and V/EC < 2, whereas V/EC > 8 excluded the influence of shipping emissions. Other ratios (V/ S, La/Ce, Zn/Ni, Pb/Zn, OC/EC) and tracers (Pb, Zn) were also tested but did not correlate with this source. Due to the changing composition of diesel fuels, tracers in the Mediterranean Sea may not be representative in other regions of the world and vice versa. The contribution of shipping emissions to ambient particulate matter (PM) urban background levels was quantified by positive matrix factorization (PMF), resulting in 2% and 4% of mean annual PM10 levels (0.8 microg/m3 primary particles and 1.7 microg/m3 secondary particles, with 20% uncertainty) and 14% of mean annual PM2.5 levels (2.6 microg/m3).