Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied. We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3-4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic. Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Atmospheric deposition of chlorinated and brominated polycyclic aromatic hydrocarbons in central Europe analyzed by GC-MS/MS.

Chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) are persistent organic pollutants that are ubiquitous in the atmospheric environment. The sources, fate, and sinks in the atmosphere of these substances are largely unknown. One of the reasons is the lack of widely accessible analytical instrumentation. In this study, a new analytical method for ClPAHs and BrPAHs using gas-chromatography coupled with triple quadrupole mass spectrometry is presented. The method was applied to determine ClPAHs and BrPAHs in total deposition samples collected at two sites in central Europe. Deposition fluxes of ClPAHs and BrPAHs ranged 580 (272-962) and 494 (161-936) pg m-2 day-1, respectively, at a regional background site, Kosetice, and 547 (351-724) and 449 (202-758) pg m-2 day-1, respectively, at a semi-urban site, Praha-Libus. These fluxes are similar to those of PCBs and more than 2 orders of magnitude lower than those of the parent PAHs in the region. Seasonal variations of the deposition fluxes of these halogenated PAHs were found with maxima in summer and autumn, and minima in winter at Kosetice, but vice versa at Praha-Libus. The distribution of ClPAHs and BrPAHs between the particulate and dissolved phases in deposition samples suggests higher degradability of particulate BrFlt/Pyr and BrBaA than of the corresponding ClPAHs. A number of congeners were detected for the first time in the atmospheric environment.

Three years of atmospheric concentrations of nitrated and oxygenated polycyclic aromatic hydrocarbons and oxygen heterocycles at a central European background site.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs, OPAHs) are abundant in the atmosphere and contribute significantly to the health risk associated with inhalation of polluted air. Despite the health hazard they pose, NPAHs and OPAHs were rarely included in monitoring. The aim of this study is to provide the first multi-year temporal trends of the concentrations, composition pattern and fate of NPAHs and OPAHs in air from a site representative of background air quality conditions in central Europe. Samples were collected every second week at a rural background site in the Czech Republic during 2015-2017. Concentrations ranged from 1.3 to 160 pg m-3 for Σ17NPAHs, from 32 to 2600 pg m-3 for Σ10OPAHs and from 5.1 to 4300 pg m-3 for Σ2O-heterocycles. The average particulate mass fraction (θ) ranged from 0.01 ± 0.02 (2-nitronaphthalene) to 0.83 ± 0.22 (1-nitropyrene) for individual NPAHs and from <0.01 ± 0.01 (dibenzofuran) to 0.96 ± 0.08 (6H-benzo (c,d)pyren-6-one) for individual OPAHs and O-heterocycles. The multiyear variations showed downward trends for a number of targeted compounds. This suggests that on-going emission reductions of PAHs are effective also for co-emitted NPAHs and OPAHs.

Bulk atmospheric deposition of persistent organic pollutants and polycyclic aromatic hydrocarbons in Central Europe.

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for Σ15PAHs ranged 23-1100 ng m-2 d-1, while those for Σ6PCBs and Σ12OCPs ranged 64-4400 and 410-7800 pg m-2 d-1, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase.