Spatiotemporal Gradients of PAH Concentrations in Greek Cities and Associated Exposure Impacts.

To study the spatiotemporal variability of particle-bound polycyclic aromatic hydrocarbons (PAHs) and assess their carcinogenic potential in six contrasting urban environments in Greece, a total of 305 filter samples were collected and analyzed. Sampling sites included a variety of urban background, traffic (Athens, Ioannina and Heraklion), rural (Xanthi) and near-port locations (Piraeus and Volos). When considering the sum of 16 U.S. EPA priority PAHs, as well as that of the six EU-proposed members, average concentrations observed across locations during summer varied moderately (0.4-2.2 ng m-3) and independently of the population of each site, with the highest values observed in the areas of Piraeus and Volos that are affected by port and industrial activities. Winter levels were significantly higher and more spatially variable compared to summer, with the seasonal enhancement ranging from 7 times in Piraeus to 98 times in Ioannina, indicating the large impact of PAH emissions from residential wood burning. Regarding benzo(a)pyrene (BaP), an IARC Group 1 carcinogen and the only EU-regulated PAH, the winter/summer ratios were 24-33 in Athens, Volos, Heraklion and Xanthi; 60 in Piraeus; and 480 in Ioannina, which is afflicted by severe wood-burning pollution events. An excellent correlation was observed between organic carbon (OC) and benzo(a)pyrene (BaP) during the cold period at all urban sites (r2 > 0.8) with stable BaP/OC slopes (0.09-0.14 × 10-3), highlighting the potential use of OC as a proxy for the estimation of BaP in winter conditions. The identified spatiotemporal contrasts, which were explored for the first time for PAHs at such a scale in the Eastern Mediterranean, provide important insights into sources and controlling atmospheric conditions and reveal large deviations in exposure risks among cities that raise the issue of environmental injustice on a national level.

Water soluble reactive phosphate (SRP) in atmospheric particles over East Mediterranean: The importance of dust and biomass burning events.

The importance of dust and biomass burning episodes on the atmospheric concentration of water-soluble reactive phosphate (SRP) was determined in the eastern Mediterranean. SRP was measured with a new rapid real-time automated analytical system with a time resolution of a few minutes per sample and with an extremely low detection limit. The average atmospheric concentration of SRP during the sampling campaign was estimated at 0.35 ± 0.25 (median 0.30) nmol P m-3. The maximum concentration of SRP (3.08 nmol P m-3) was recorded during an intense dust episode, and was almost ten times higher than the campaign average, confirming that Saharan dust was an important primary source of bioavailable P to the eastern Mediterranean, especially during the spring period when 60% of the events occurred. Predicted increases in the frequency and intensity of dust storms in the area will enhance the role of the atmosphere as a source of bioavailable P for the Mediterranean marine ecosystem. During the warm period, when Northerly winds prevailed, biomass burning processes contributed significantly to soluble phosphorus delivered from atmospheric sources to the eastern Mediterranean. These inputs during warm periods are especially important for the Eastern Mediterranean, where biological productivity is strongly limited by nutrient availability.

Effects of Atmospheric Processing on the Oxidative Potential of Biomass Burning Organic Aerosols.

Oxidative potential (OP), which is the ability of certain components in atmospheric particles to generate reactive oxidative species (ROS) and deplete antioxidants in vivo, is a prevailing toxicological mechanism underlying the adverse health effects associated with exposure to ambient aerosols. While previous studies have identified the high OP of fresh biomass burning organic aerosols (BBOA), it remains unclear how it evolves throughout atmospheric transport. Using the dithiothreitol (DTT) assay as a measure of OP, a combination of field observations and laboratory experiments is used to determine how atmospheric aging transforms the intrinsic OP (OPmassDTT) of BBOA. For ambient BBOA collected during the fire seasons in Greece, OPmassDTT was observed to increase by a factor of 2.1 ± 0.9 for samples of atmospheric ages up to 68 h. Laboratory experiments indicate that aqueous photochemical aging (aging by UVB and UVA photolysis; as well as OH oxidation), as well as aging by ozone and atmospheric dilution can transform the OPmassDTT of the water-soluble fraction of wood smoke within 2 days of atmospheric transport. The results from this work suggest that the air quality impacts of biomass burning emissions can extend beyond regions near fire sites and should be accounted for.