Chemical characterization, sources and potential health risk of PM2.5 and PM1 pollution across the Greater Athens Area.

With the principal aim to assess the typical Mediterranean profile of the PM2.5 and PM1 pollution, three intensive monitoring campaigns took place simultaneously within different types of environment across an urban location of the basin. Focusing on the PM components with numerous anthropogenic sources and increased potential health risk, the samples were chemically analyzed for 20 p.m.-bound Polycyclic Aromatic Hydrocarbons (PAHs). Carbonaceous and ionic constituents were quantified as well. In order to uncover the spatiotemporal variation of the PM profile the key sources were identified, the seasonal effects and the role of the prevailing mesoscale atmospheric circulation were evaluated and most importantly the potential health risk was estimated. In general, the pollution status of the basin was the result of a complex interaction between the local and external input with Particulate Organic Matter (POM) and Secondary Inorganic Aerosols (SIA) being the main aerosols' components. PM1 was a better indicator of the anthropogenic emissions while according to the results of factor analysis the co-existence of various combustion sources was determinant. Chemically, the maxima of the ΣPAHs, the differentiation of their structure in accordance with their molecular weight and the distribution of the individual compounds confirmed the significance of the emission sources. Similarly, the estimated carcinogenicity/mutagenicity was emission-dependent with the maximum contribution coming from B[a]P, IndP, B[ghi]Per, B[e]P and B[b]F. Seasonally, the highest potential health risk of the PAHs' mixture was recorded during the cold season while meteorologically, it was mostly associated with the south flow.

The traffic signature on the vertical PM profile: Environmental and health risks within an urban roadside environment.

In an attempt to investigate the traffic-impacted vertical aerosols profile and its relationship with potential carcinogenicity and/or mutagenicity, samples of different sized airborne particles were collected in parallel at the 1st and 5th floor of a 19 m high building located next to one of the busiest roads of Athens. The maximum daily concentrations were 65.9, 42.5 and 38.5 µg/m3, for PM10, PM2.5 and PM1, respectively. The vertical concentration ratio decreased with increasing height verifying the role of the characteristics of the area (1st/5th floor: 1.21, 1.13, 1.09 for PM10, PM2.5 and PM1, respectively). Chemically, strengthening the previous hypothesis, the collected particles were mainly carbonaceous (68%-93%) with the maximum budget of the polyaromatic hydrocarbons being recorded near the surface (1st/5th floor: 1.84, 1.07, 1.15 for PM10, PM2.5 and PM1, respectively). The detected PM-bound PAHs along with the elements as well as the carbonaceous and ionic constituents were used in a source apportionment study. Exhaust and non-exhaust emissions, a mixed source of biomass burning and high temperature combustion processes (natural gas, gasoline/diesel engines), sea salt, secondary and soil particles were identified as the major contributing sources to the PM pollution of the investigated area. With respect to the health hazards, the calculation of the Benzo[a]Pyrene toxicity equivalency factors underlined the importance of the height of residence in buildings for the level of the exposure (1st/5th floor: B[a]PTEQ: 1.82, 1.12, 1.10, B[a]PMEQ: 1.85, 1.13, 1.09 for PM10, PM2.5 and PM1, respectively). Finally, despite its verified significance as a surrogate compound for the mixture of the hydrocarbons (its contribution up to 72%, 79% on the level of the 1st and 5th floor, respectively), the importance of the incorporation of PAH species in addition to B[a]P when assessing PAH toxicity was clearly documented.

Assessment of PM2.5 and PM1 chemical profile in a multiple-impacted Mediterranean urban area: origin, sources and meteorological dependence.

Airborne particulate matter in the PM2.5 and PM1 size ranges has been sampled at three sites within the Mediterranean urban area of the Athens Basin, representing background, roadside-industrialized and coastal background locations. With the principal aim to identify the sources and discriminate the contribution of the regional input versus the local one, simultaneous chemical characterization with respect to carbonaceous and ionic species was also carried out on the collected samples. In general, the average recorded values were within the Mediterranean concentration range. The constant prevalence of the ionic mass (52%-79%) over one of the carbonaceous, being combined with the occurrence of its maximum rates at the coastal background environment (74%-79% and 73%-77% for PM2.5 and PM1, respectively) leads to the hypothesis that the fine PM pollution in the basin, especially for the remote locations, is evidently governed by the external intrusion. Even at the polluted atmosphere of the roadside-industrialized environment, the PM mass was regionally originated, with the corresponding input reaching up to 87% (northward flow). Applying factor analysis on the PM2.5 database it came obvious that the sources which were responsible for the configured PM burden were not fully differentiated not only between the different types of environment but also between the exceedances and the clean air events. The contribution of the secondary, marine and combustion processes was constant at all the stations of the network, while a continuous input of crustal particles characterized both the roadside-industrialized and the coastal atmosphere. Finally, the episodic values show a general common signal of secondary mixed ΡΜ emissions, high influence of both regional and local pollution spikes, confirming the earlier findings for the significance of transportation.

Particulate matter pollution over a Mediterranean urban area.

The main purpose of this study is to investigate the aerosols' (PM10, PM2.5, and PM1) spatial and temporal distribution in different types of environment in a Mediterranean urban region, the Greater Athens Area based on data from a sampling campaign that took place during the cold and warm period of 2008. The influence of the atmospheric circulation patterns, the possible local transport mechanisms, as well as the differentiation of the PM behaviour from that of the inorganic pollutants (NOx, O3), are analysed and discussed. Furthermore, the Comprehensive Air Quality Model with extensions (CAMx) was applied for selected sampling dates and its results were evaluated against measurements in order to interpret qualitatively the configured picture of the air pollution above the GAA. Analysis of the measurement data show that local sources such as traffic and industry dominate over the prevailing PM loads, especially at the 'hot spot' areas. Moreover, the synoptic circulation patterns associated with calm conditions and southerly flows lead to high particulate pollution levels that also affect the urban background stations. Saharan dust outbreaks appeared to increase the particles' diameter as well as the number of E.U. limit value exceedances within the stations of our network. Without any dependence on the characteristics of the investigated atmosphere, PM1 always constituted the greatest part of the PM2.5 mass while PM10, especially during the Saharan dust episodes, was mainly constituted by the coarse fraction. The numerical modelling approach of the geographical distribution of PM10, PM2.5, NOx and O3 justified the design of the sampling campaign, indicating the need for the systematic and parallel monitoring and modelling of the pollutants' dispersion in order to understand the particulate pollution problem in the GAA and to aid to the formulation of pollution control strategies.

Carbonaceous and ionic compositional patterns of fine particles over an urban Mediterranean area.

A carefully designed experimental study based on the monitoring of fine airborne particles, was carried out at three different locations (suburban background, traffic-industrial, coastal background) of an urban Mediterranean area, the Athens Basin. Understanding of the PM(2.5) and PM(1) nature has an important policy implication. In total, five hundred and nineteen samples were chemically analyzed with respect to carbonaceous (organic/elemental carbon) and ionic (NH(4)(+), K(+), Mg(2+), Ca(2+), NO(3)(-), Cl(-), SO(4)(2-)) species. The dataset consists one of the very few in the Mediterranean which simultaneously deals with the carbonaceous and ionic components of fine aerosol fractions, especially for PM(1). Daily PM(2.5) averages often exceeded the E.U. limit values, with their mass being mainly composed of PM(1). The most important constituents of secondary particles were SO(4)(2-) and organic carbon, with both accounting for 56.4%-64.3% and 60.5%-62.3% of the total PM(2.5) and PM(1) mass, respectively. Regional sources, marine/crustal elements, combustion sources and traffic were indicated by factor analysis as the greatest contributors to the mass of both PM(2.5) and PM(1) fractions, accounting for 85.3% and 83.6%, respectively of the total variance in the system. It is worthy to note, the key role of the prevailing atmospheric conditions to the configuration of the obtained picture of the particulate pollution.

The role of meteorology on different sized aerosol fractions (PM10, PM2.5, PM2.5-10).

The scope of the present study is to assess the influence of meteorology on different diameter particles (PM(10), PM(2.5), PM(2.5-10)) during a 53 months long experimental campaign at an urban Mediterranean area. Except for the investigation of the wind, temperature and relative humidity role, day by day synoptic conditions were classified over the Attica peninsula in order to explore as well, the role of the synoptic scale atmospheric circulation. The strong dependence of the aerosols character on their various sources, not only explain the different diameter particles behavior and their differentiation with the inorganic pollutants but also highlights the need for an effective emission policy. High PM(10) and PM(2.5-10) concentrations found to be closely related to the southwesterly regime, suggesting long range transport from the 'polluted' south sector while the general prevalence of the secondary particles generation revealed the health hazard. PM(2.5) showed a weaker correlation than the bigger particles with both the circulation patterns and the parameters' fluctuations. Temporal pollutants variations were clearly governed by the emissions patterns while the low wind speed was not necessarily a good indicator of high concentration levels. Finally it was found that only during the open/close anticyclonic days and the southwesterly wind regime the morning levels were continuously higher than those of the night.

Particulate matter levels in a suburban Mediterranean area: analysis of a 53-month long experimental campaign.

Parallel measurements of ambient particulate matter mass in terms of PM(10), PM(2.5) and PM(2.5-10), conducted during a 53 months long experiment, between 2003 and 2008. The data constituting one of the longest simultaneous comparative data sets for the three PM fractions in Europe, collected at a suburban area of Athens, Aghia Paraskevi. Total means of mass concentrations for PM(10), PM(2.5) and PM(2.5-10) were in the order of 34.8, 18.0 and 23.8 microg/m(3), respectively. Seasonal variability of PM levels governed by the fact that the specific site is dominated by secondary aerosol emissions with the concentrations presenting a shift to the warm period. During the whole sampling period PM(10) were mainly composed of PM(2.5) while particles with the bigger diameter proved to be strongly correlated in all the cases. It would be interesting to mention that all the three aerosol fractions did not present any association with the inorganic pollutants. Stagnant conditions as well as the wind direction proved to be key mechanisms for the configuration of the air quality patterns. Saronic Gulf sea-breeze development enhanced the aerosol transportation from the industrialized greater area of Piraeus and the polluted center of the city, to the Northern suburbs.

PM2.5 and volatile organic compounds (VOCs) in ambient air: a focus on the effect of meteorology.

PM(2.5) and VOCs (benzene, toluene, m-p-o-xylenes) concentrations were measured in an urban and a suburban site in Athens, Greece, during the period between April and November 2004. This period, which is considered to be the warmer period in Greece, is characterized by the development of sea-breeze over the Attica Basin. Additionally strong Northern, North-eastern winds called "The Etesians", predominate during the summer months (July-August), acting positively to the dispersion of pollutants. In this campaign, 24 days with sea-breeze development were observed, 15 days with northern winds, 6 days with southern winds while the rest of the days presented no specific wind profile. Maximum concentrations of PM(2.5), VOCs and nitrogen oxides, were detected during the days with sea-breeze, while minimum concentrations during the days with northern winds. Ozone was the only pollutant that appeared to have higher concentrations in the background site and not in the city centre, where benzene presented strong negative correlation with ozone, indicating the photochemical reaction of hydrocarbons that lead to the ozone formation. The BTX ratios were similar for both sites and wind profiles, indicating common sources for those pollutants. T/B ratio ranged in low levels, between 3-5 for site A and 2-5 for site B, suggesting vehicles emissions as the main sources of volatile compounds. Finally, the strong correlations of PM(2.5) and benzene concentrations, between the two sampling sites, indicate that both the city centre and the background site, are affected by the same sources, under common meteorological conditions (sea-breeze, northern winds).

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region.

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.

Photocatalytic degradation of NOx in a pilot street canyon configuration using TiO2-mortar panels.

Titanium dioxide is the most important photocatalysts used for purifying applications. If a TiO2- containing material is left outdoors as a form of flat panels, it is activated by sunlight to remove harmful NOx gases during the day. The photocatalytic efficiency of a TiO2-treated mortar for removal of NOx was investigated in the frame of this work. For this purpose a fully equipped monitoring system was designed at a pilot site. This system allows the in situ evaluation of the de-polluting properties of a photocatalytic material by taking into account the climatologic phenomena in street canyons, accurate measurements of pollution level and full registration of meteorological data The pilot site involved three artificial canyon streets, a pollution source, continuous NOx measurements inside the canyons and the source as well as background and meteorological measurements. Significant differences on the NOx concentration level were observed between the TiO2 treated and the reference canyon. NOx values in TiO2 canyon were 36.7 to 82.0% lower than the ones observed in the reference one. Data arising from this study could be used to assess the impact of the photocatalytic material on the purification of the urban environment.

Gas-particle concentration and characterization of sources of PAHs in the atmosphere of a suburban area in Athens, Greece.

Atmospheric polycyclic aromatic hydrocarbons (PAH) were determined in two places in a suburban area of Athens greater area (AGA) during June and November 2003. Fourteen PAHs were quantified in the collected samples. The total concentration in the gas phase ranged between 6.89 and 124ngm(-3), while in the particulate phase between 0.44 and 13.2ngm(-3). Maximum concentrations of the total PAHs (gas and particulate phase) were observed during the cold period with an average of 40.7ngm(-3). PAHs were correlated with NO, NO(2) and O(3), wind speed, wind direction and temperature. Positive correlation was observed between PAHs and NO, NO(2), while negative correlation was detected between PAHs and O(3). The most abundant members were phenanthrene, anthracene, fluorene, fluoranthene and pyrene. Potential sources of PAHs in aerosols were investigated using molecular diagnostic ratios, which reflect sources such as diesel and gasoline engines, although other sources such as coal combustion and liquefied petroleum gas also contributed.