Abstract. Polycyclic aromatic hydrocarbons (PAHs), their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants has hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑27PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phase, were 2.85 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as Persian Gulf). 1,4 Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2 nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-NFLT, which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-nitrofluoranthene (2-NFLT) and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, also benz(a)anthracene-7,12-dione and 1,4-O2NAP had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).
Abstract. This study presents multi-year monitoring data on atmospheric polybrominated diphenyl ethers (PBDEs) in central Europe. Air was sampled on a weekly basis at a background site in the central Czech Republic from 2011 to 2014 (N = 114). Σ8PBDEs (without BDE209) total (gas and particulate) concentrations ranged from 0.084 to 6.08 pg m−3, while BDE209 was at 0.05–5.01 pg m−3. BDE47, BDE99 and BDE183 were the major contributors to Σ8PBDEs.Overall, the atmospheric concentrations of individual PBDEs were controlled by deposition processes, meteorological parameters and long-range atmospheric transport. Regarding gas–particle partitioning, with the exception of BDE28 (gaseous) and BDE209 (particulate), all congeners were consistently detected in both phases. Clear seasonal variations with significantly higher measured particulate fraction (θmeasured) in winter compared to summer was found for all PBDEs except BDE209. For example, while the average θmeasured of BDE47 was 0.53±0.19 in winter, this was only 0.01±0.02 in summer. Similarly, for BDE99, θmeasured was 0.89±0.13 in winter, while it was only 0.12±0.08 in summer. The observed gas–particle partitioning coefficient (Kp, in m3 µg−1) was compared with three model predictions, assuming equilibrium or a steady state. None of the models could provide a satisfactory prediction of the partitioning, suggesting the need for a universally applicable model.Statistically significant decreases of the atmospheric concentrations during 2011–2014 were found for BDE99, 100, 153 and 209. Estimated apparent atmospheric halving times for these congeners ranged from 2.8 (BDE209) to 4.8 (BDE153) years. The results suggest that photolytic debromination to lower brominated congeners may significantly influence PBDE concentration levels and patterns in the atmosphere.
Abstract Neben der Beobachtung von Chemikalien in den Umweltkompartimenten, insbesondere fern der Emissionen, sind Fortschritte bei Probennahme, Analytik und physikalischer Messtechnik die wichtigsten Impulsgeber umweltchemischer Forschung. In der Atmosphärenchemie gewinnen Satelliten als messtechnische Plattformen an Bedeutung. Aerosole und Wolken werden verstärkt untersucht. Sensationell ist, dass Polymerisationsreaktionen in den Partikeln des atmosphärischen Aerosols Teil der natürlichen Luftchemie sind.
Abstract Redox-active substances in fine particulate matter (PM) contribute to inhalation health risks through their potential to generate reactive oxygen species in epithelial lung lining fluid (ELF). The ELF’s air–liquid interface (ALI) can play an important role in the phase transfer and multi-phase reactions of redox-active PM constituents. We investigated the influence of interfacial processes and properties by scrubbing of coated nano-particles with simulated ELF in a nebulizing mist chamber. Weakly water-soluble redox-active organics abundant in ambient fine PM were reproducibly loaded into ELF via ALI mixing. The resulting oxidative potential (OP) of selected quinones and other PAH derivatives were found to exceed the OP resulting from bulk mixing of the same amounts of redox-active substances and ELF. Our results indicate that the OP of PM components depends not only on the PM substance properties but also on the ELF interface properties and uptake mechanisms. OP measurements based on bulk mixing of phases may not represent the effective OP in the human lung.
Polycyclic aromatic hydrocarbons (PAHs) in the atmospheric environment are almost exclusively formed in combustion processes. Oxygenated and nitrated PAHs are co-emitted with parent PAHs from fossil fuel and biomass combustion processes, and many are formed in photochemical and microbiological reactions of PAHs in air and soil. As semivolatiles resisting biodegradation in soils and surface waters to some extent, polycyclic aromatic compounds (PACs) i.e., PAHs and their derivatives, can be subject to re-volatilisation., which may turn soils and surface waters from sinks into secondary sources and enhances the long-range transport potential of PACs by multihopping (grasshopper effect). The significance of these secondary sources for PAC abundances in ambient air is unknown and is not accounted for in emission inventories. Gaps in PAH emission inventories have been indicated by field studies in various countries. We determined the concentrations of 15 parent, 10 oxygenated and 17 nitrated PAHs in air and soils at a rural and near-coastal northern European site and a central European rural background site, and in air and surface seawater at two off-shore sites in the eastern Mediterranean and along NW-SE transects in the Mediterranean. Directions of air-soil and air-sea exchanges were derived from the substances’ fugacities. At the central European site, a number of 2-4 ring PACs were found to volatilise from grassland and more from forest soils in summer, and much less in winter. Conversely, at the receptor site in northern Europe, net deposition of PACs prevails and re-volatilisation occurs only sporadically. In the Mediterranean, 3-4 ring PAHs and dibenzofuran are found to volatilise in most seasons. Existing data on air-surface exchange of PACs is notably scarce, and methodological uncertainties persist in quantifying air-soil exchange. As very little is known about the spatial and seasonal distributions of PACs soil burdens and net mass fluxes, an assessment of the significance of soils and surface waters as secondary sources of PACs in the air of source and receptor areas is not possible.  
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