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.

Recommendations for reporting equivalent black carbon (eBC) mass concentrations based on long-term pan-European in-situ observations.

A reliable determination of equivalent black carbon (eBC) mass concentrations derived from filter absorption photometers (FAPs) measurements depends on the appropriate quantification of the mass absorption cross-section (MAC) for converting the absorption coefficient (babs) to eBC. This study investigates the spatial-temporal variability of the MAC obtained from simultaneous elemental carbon (EC) and babs measurements performed at 22 sites. We compared different methodologies for retrieving eBC integrating different options for calculating MAC including: locally derived, median value calculated from 22 sites, and site-specific rolling MAC. The eBC concentrations that underwent correction using these methods were identified as LeBC (local MAC), MeBC (median MAC), and ReBC (Rolling MAC) respectively. Pronounced differences (up to more than 50 %) were observed between eBC as directly provided by FAPs (NeBC; Nominal instrumental MAC) and ReBC due to the differences observed between the experimental and nominal MAC values. The median MAC was 7.8 ± 3.4 m2 g-1 from 12 aethalometers at 880 nm, and 10.6 ± 4.7 m2 g-1 from 10 MAAPs at 637 nm. The experimental MAC showed significant site and seasonal dependencies, with heterogeneous patterns between summer and winter in different regions. In addition, long-term trend analysis revealed statistically significant (s.s.) decreasing trends in EC. Interestingly, we showed that the corresponding corrected eBC trends are not independent of the way eBC is calculated due to the variability of MAC. NeBC and EC decreasing trends were consistent at sites with no significant trend in experimental MAC. Conversely, where MAC showed s.s. trend, the NeBC and EC trends were not consistent while ReBC concentration followed the same pattern as EC. These results underscore the importance of accounting for MAC variations when deriving eBC measurements from FAPs and emphasize the necessity of incorporating EC observations to constrain the uncertainty associated with eBC.

Source apportionment of fine and ultrafine particle number concentrations in a major city of the Eastern Mediterranean.

Ultrafine particles (UFP) are recognized as an emerging pollutant able to induce serious health effects. However, quantitative information regarding the contributions of UFP sources is generally limited. This study evaluates statistical (k-means clustering) and receptor models (Positive Matrix Factorization - PMF) using particle number size distributions (PNSD), along with chemical speciation data, measured at an urban background supersite in Athens, Greece, aiming to characterize their sources. PNSD measurements (10-487 nm) were performed during three distinct periods (warm, cold, and lockdown cold). Traffic and residential biomass burning (BB) produced high UFP number concentrations (NUFP) in the cold period (+107 % compared to summer), while the lockdown restrictions reduced NUFP (-42 %). The five groups produced by cluster analysis that were common among periods were linked to high- and low-traffic, new particle formation (NPF), urban background and regional aerosols. PMF source apportionment identified 5 and 6 factors during warm and cold periods, respectively, indicating that traffic particles dominated NUFP (64-78 % in all periods), while accumulation-mode particles and volume concentrations were controlled by processed aerosol, and especially in the cold periods by BB emissions. A nucleation factor linked to NPF contributed 7-11 % to NUFP. Comparing the two cold periods (business-as-usual, lockdown), important lockdown reductions (-46 %) were seen for fresh traffic contributions to total number concentration (Ntotal). The impact of the source attributed to NPF also eroded (-41 % for Ntotal). Due to the large reduction (-47 % for Ntotal) observed also for the BB source during the lockdown (reduced wood usage due to a milder winter), the relative contributions of all sources did not change considerably (fractional reductions <7 % for Ntotal). The quantitative results, bolstered by source apportionment combining PNSD and online chemical composition measurements, indicate the potential to constrain UFP levels by regulating traffic and residential emissions, with a large upside for population exposure control.

Emission of volatile organic compounds from residential biomass burning and their rapid chemical transformations.

Biomass combustion releases a complex array of Volatile Organic Compounds (VOCs) that pose significant challenges to air quality and human health. Although biomass burning has been extensively studied at ecosystem levels, understanding the atmospheric transformation and impact on air quality of emissions in urban environments remains challenging due to complex sources and burning materials. In this study, we investigate the VOC emission rates and atmospheric chemical processing of predominantly wood burning emissions in a small urban centre in Greece. Ioannina is situated in a valley within the Dinaric Alps and experiences intense atmospheric pollution accumulation during winter due to its topography and high wood burning activity. During pollution event days, the ambient mixing ratios of key VOC species were found to be similar to those reported for major urban centres worldwide. Positive matrix factorisation (PMF) analysis revealed that biomass burning was the dominant emission source (>50 %), representing two thirds of OH reactivity, which indicates a highly reactive atmospheric mixture. Calculated OH reactivity ranges from 5 s-1 to an unprecedented 278 s-1, and averages at 93 ± 66 s-1 at 9 PM, indicating the presence of exceptionally reactive VOCs. The highly pronounced photochemical formation of organic acids coincided with the formation of ozone, highlighting the significance of secondary formation of pollutants in poorly ventilated urban areas. Our findings underscore the pressing need to transition from wood burning to environmentally friendly sources of energy in poorly ventilated urban areas, in order to improve air quality and safeguard public health.

The variability of mass concentrations and source apportionment analysis of equivalent black carbon across urban Europe.

This study analyzed the variability of equivalent black carbon (eBC) mass concentrations and their sources in urban Europe to provide insights into the use of eBC as an advanced air quality (AQ) parameter for AQ standards. This study compiled eBC mass concentration datasets covering the period between 2006 and 2022 from 50 measurement stations, including 23 urban background (UB), 18 traffic (TR), 7 suburban (SUB), and 2 regional background (RB) sites. The results highlighted the need for the harmonization of eBC measurements to allow for direct comparisons between eBC mass concentrations measured across urban Europe. The eBC mass concentrations exhibited a decreasing trend as follows: TR > UB > SUB > RB. Furthermore, a clear decreasing trend in eBC concentrations was observed in the UB sites moving from Southern to Northern Europe. The eBC mass concentrations exhibited significant spatiotemporal heterogeneity, including marked differences in eBC mass concentration and variable contributions of pollution sources to bulk eBC between different cities. Seasonal patterns in eBC concentrations were also evident, with higher winter concentrations observed in a large proportion of cities, especially at UB and SUB sites. The contribution of eBC from fossil fuel combustion, mostly traffic (eBCT) was higher than that of residential and commercial sources (eBCRC) in all European sites studied. Nevertheless, eBCRC still had a substantial contribution to total eBC mass concentrations at a majority of the sites. eBC trend analysis revealed decreasing trends for eBCT over the last decade, while eBCRC remained relatively constant or even increased slightly in some cities.

Variability and sources of non-methane hydrocarbons at a Mediterranean urban atmosphere: The role of biomass burning and traffic emissions.

Levels and sources of non-Methane Hydrocarbons (NMHCs) were investigated at the urban background Thissio station, close to the historical center of Athens (Greece) from March 2016 to February 2017 (12 months), by means of an automated GC-FID. Alkanes dominated over aromatics and alkenes, with hourly mean levels ranging from detection limit up to 60 µg m-3 for i-pentane and 90 µg m-3 for toluene. Higher levels were recorded in the cold period relative to the warmer one. In addition, NMHCs seasonal diurnal cycles were characterized by a bimodal pattern, following the trend of tracers of anthropogenic sources. The Positive Matrix Factorization (PMF) was used for the allocation of NMHC to their sources. Five factors were identified and quantified, with traffic-related sources being the main one contributing up to 60% to total NMHCs, while biomass burning contributes up to 19%. A supplementary PMF assimilation was applied on a seasonal basis further including α-pinene, C6-C16 alkanes and aromatics. This PMF resulted to a seven-factor solution that allowed the examination of two additional sources, in addition to five already identified, highlighting the main contribution of anthropogenic sources (70%) to α-pinene.

The combined effect of reduced fossil fuel consumption and increasing biomass combustion on Athens' air quality, as inferred from long term CO measurements.

To evaluate the role of biomass burning emissions, and in particular of residential wood heating, as a result of the economic recession in Greece, carbon monoxide (CO) atmospheric concentrations from five (5) stations of the National Air Pollution Monitoring Network in Athens, spanning the period 2000-2015, in conjunction with black carbon (BC) concentrations from the NOA (National Observatory of Athens) station at Thissio were analysed. The contribution of the different sources to the diurnal cycle of these two pollutants is clear, resulting to a morning peak, mainly due to traffic, and a late evening peak attributed both to fossil fuel (traffic plus central heating) and biomass combustion. Calculated morning and evening integrals of CO peaks, for the investigated period, show consistent seasonal modulations, characterised by low summer and high winter values. The summer and winter morning CO peak integrals demonstrate an almost constant decreasing trend of CO concentrations over time (by almost 50% since 2000), attributed to the renewal of passenger car fleet and to reduced anthropogenic activities during the last years. On the other hand, an increase of 23%-78% (depending on the monitoring site) in the winter evening integrals since 2012, provides evidence of the significant contribution of biomass combustion, which has prevailed over fossil fuel for domestic heating. CO emitted by wood burning was found to contribute almost 50% to the total CO emissions during night time (16:00-5:00), suggesting that emissions from biomass combustion have gained an increasing role in atmospheric pollution levels in Athens.