Quantitative assessment of the variability in chemical profiles from source apportionment analysis of PM10 and PM2.5 at different sites within a large metropolitan area.

The study aims to assess the differences between the chemical profiles of the major anthropogenic and natural PM sources in two areas with different levels of urbanization and traffic density within the same urban agglomeration. A traffic site and an urban background site in the Athens Metropolitan Area have been selected for this comparison. For both sites, eight sources were identified, with seven of them being common for the two sites (Mineral Dust, non-Exhaust Emissions, Exhaust Emissions, Heavy Oil Combustion, Sulfates & Organics, Sea Salt and Biomass Burning) and one, site-specific (Nitrates for the traffic site and Aged Sea Salt for the urban background site). The similarity between the source profiles was quantified using two statistical analysis tools, Pearson correlation (PC) and Standardized Identity Distance (SID). According to Pearson coefficients five out of the eight source profiles present high (PC > 0.8) correlation (Mineral Dust, Biomass Burning, Sea Salt, Sulfates and Heavy Oil Combustion), one presented moderate (0.8 > PC > 0.6) correlation (Exhaust) and two low/no (PC < 0.6) correlation (non-Exhaust, Nitrates/Aged Sea Salt). The source profiles that appear to be more correlated are those of sources that are not expected to have high spatial variability because there are either natural/secondary and thus have a regional character or are emitted outside the urban agglomeration and are transported to both sites. According to SID four out of the eight sources have high statistical correlation (SID < 1) in the two sites (Mineral Dust, Sea salt, Sulfates, Heavy Oil Combustion). Biomass Burning was found to be the source that yielded different results from the two methodologies. The careful examination of the source profile of that source revealed the reason for this discrepancy. SID takes all the species of the profile equally into account, while PC might be disproportionally affected by a few numbers of species with very high concentrations. It is suggested, based on the findings of this work, that the combined use of both tools can lead the users to a thorough evaluation of the similarity of source profiles. This work is, to the best of our knowledge, the first time a study is focused on the quantitative comparison of the source profiles for sites inside the same urban agglomeration using statistical indicators.

Estimating the concentration of indoor particles of outdoor origin: a review.

Recent toxicological results highlight the importance of separating exposure to indoor- and outdoor-generated particles, due to their different physicochemical and toxicological properties. In this framework, a number of studies have attempted to estimate the relative contribution of particles of indoor and outdoor origins to indoor concentrations, using either statistical analysis of indoor and outdoor concentration time-series or mass balance equations. The aim of this work is to review and compare the methodologies developed in order to determine the ambient particle infiltration factor (F(INF)) (i.e., the fraction of ambient particles that enter indoors and remains suspended). The different approaches are grouped into four categories according to their methodological principles: (1) steady-state assumption using the steady-state form of the mass balance equation; (2) dynamic solution of the mass balance equation using complex statistical techniques; (3) experimental studies using conditions that simplify model calculations (e.g., decreasing the number of unknowns); and (4) infiltration surrogates using a particulate matter (PM) constituent with no indoor sources to act as surrogate of indoor PM of outdoor origin. Examination of the various methodologies and results reveals that estimating infiltration parameters is still challenging. The main difficulty lies in the separate calculation of penetration efficiency (P) and deposition rate (k). The values for these two parameters that are reported in the literature vary significantly. Deposition rate presents the widest range of values, both between studies and size fractions. Penetration efficiency seems to be more accurately calculated through the application of dynamic models. Overall, estimates of the infiltration factor generated using dynamic models and infiltration surrogates show good agreement. This is a strong argument in favor of the latter methodology, which is simple and easy to apply when chemical speciation data are available.

Assessment of children's exposure to carbonaceous matter and to PM major and trace elements.

Particulate matter (PM) pollution is one of the major environmental concerns due to its harmful effects on human health. As children are particularly vulnerable to particle exposure, this study integrates the concentration of PM chemical compounds measured in the micro-environments (MEs) where children spend most of their time to assess the daily exposure and inhaled dose. PM samples were analysed for organic and elemental carbon and for major and trace elements. Results showed that the MEs that contribute most to the children's daily exposure (80%) and inhaled dose (65%) were homes and schools. Results indicated that the high contribution of particulate organic matter (POM) indoors indicate high contributions of indoor sources to the organic fraction of the particles. The highest concentrations of PM chemical compounds and the highest Indoor/Outdoor ratios were measured in schools, where the contribution of mineral elements stands out due to the resuspension of dust caused by the students and to the chalk used in blackboards. The contribution of the outdoor particles to inhaled dose (24%) was higher than to the exposure (12%), due to the highest inhalation rates associated with the activities performed outdoor. This study indicates the importance of indoor air quality for the children's exposure and health.

Particle exposure and inhaled dose while commuting in Lisbon.

While commuting, individuals are exposed to high concentrations of urban air pollutants that can lead to adverse health effects. This study aims to assess commuters' exposure to particulate matter (PM) when travelling by car, bicycle, metro and bus in Lisbon. Mass concentrations of PM2.5 and PM10 were higher in the metro. On the other hand, the highest BC and PN0.01-1 average concentrations were found in car and bus mode, respectively. In cars, the outdoor concentrations and the type of ventilation appeared to affect the indoor concentrations. In fact, the use of ventilation led to a decrease of PM2.5 and PM10 concentrations and to an increase of BC concentrations. The highest inhaled doses were mostly observed in bicycle journeys, due to the longest travel periods combined with enhanced physical activity and, consequently, highest inhalation rates.

Ambient particulate matter source apportionment using receptor modelling in European and Central Asia urban areas.

This work presents the results of a PM2.5 source apportionment study conducted in urban background sites from 16 European and Asian countries. For some Eastern Europe and Central Asia cities this was the first time that quantitative information on pollution source contributions to ambient particulate matter (PM) has been performed. More than 2200 filters were sampled and analyzed by X-Ray Fluorescence (XRF), Particle-Induced X-Ray Emission (PIXE), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to measure the concentrations of chemical elements in fine particles. Samples were also analyzed for the contents of black carbon, elemental carbon, organic carbon, and water-soluble ions. The Positive Matrix Factorization receptor model (EPA PMF 5.0) was used to characterize similarities and heterogeneities in PM2.5 sources and respective contributions in the cities that the number of collected samples exceeded 75. At the end source apportionment was performed in 11 out of the 16 participating cities. Nine major sources were identified to have contributed to PM2.5: biomass burning, secondary sulfates, traffic, fuel oil combustion, industry, coal combustion, soil, salt and "other sources". From the averages of sources contributions, considering 11 cities 16% of PM2.5 was attributed to biomass burning, 15% to secondary sulfates, 13% to traffic, 12% to soil, 8.0% to fuel oil combustion, 5.5% to coal combustion, 1.9% to salt, 0.8% to industry emissions, 5.1% to "other sources" and 23% to unaccounted mass. Characteristic seasonal patterns were identified for each PM2.5 source. Biomass burning in all cities, coal combustion in Krakow/POL, and oil combustion in Belgrade/SRB and Banja Luka/BIH increased in Winter due to the impact of domestic heating, whereas in most cities secondary sulfates reached higher levels in Summer as a consequence of the enhanced photochemical activity. During high pollution days the largest sources of fine particles were biomass burning, traffic and secondary sulfates.

East Siberian Arctic background and black carbon polluted aerosols at HMO Tiksi.

Assessment of Arctic pollution is hampered by a lack of aerosol studies in Northern Siberia. Black carbon observations were carried out at the Hydrometeorological Observatory Tiksi, a coast of Laptev sea, from September 2014 to September 2016. Aerosol sampling was accompanied by physico-chemical characterization. BC climatology showed a seasonal variation with highest concentrations from January to March (up to 450ng/m3) and lowest ones for June and September (about 20ng/m3). Stagnant weather and stable atmosphere stratification resulted in accumulation of pollution, in dependence on the wind direction and air mass transportation. Carbon fractions, functionalities, ions, and elements are associated to marine, biogenic, and continental sources. In September low OC, aliphatic, carbonyls, amines, and hydroxyls characterize background aerosols. Na+/Cl- ratio much higher than in sea-salt indicates a strong Cl depletion. Increased OC, aromatic, carbonyls, and nitrocompounds as well as waste burning markers K+, Cl-, and PO42- confirm impacts from Tiksi landfill burns. BC pollution episodes are differentiated through increased EBC and sulfates, related to gas flaring, industrial and residential emissions transported from Western Siberia while the increase of carbonyls, hydroxyl, and aromatic indicate emissions sources from Yakutia and Tiksi urban area. Arctic Haze aerosols are characterized by increased concentrations of SO42- in comparison with OC, much higher abundance of oxygenated compounds with respect to alkanes of anthropogenic origin. In summer rich organic chemistry indicates impacts of biogenic, local urban, and shipping sources as well as secondary aerosol formation influenced by emissions from low latitude Siberia.

Indoor and outdoor PM mass and number concentrations at schools in the Athens area.

Simultaneous indoor and outdoor PM10 and PM2.5 concentration measurements were conducted in seven primary schools in the Athens area. Both gravimetric samplers and continuous monitors were used. Filters were subsequently analyzed for anion species. Moreover ultrafine particles number concentration was monitored continuously indoors and outdoors. Mean 8-hr PM10 concentration was measured equal to 229 +/- 182 microg/m3 indoors and 166 +/- 133 microg/m3 outdoors. The respective PM2.5 concentrations were 82 +/- 56 microg/m3 indoors and 56 +/- 26 microg/m3 outdoors. Ultrafine particles 8-h mean number concentration was measured equal to 24,000 +/- 17,900 particles/cm3 indoors and 32,000 +/- 14,200 particles/cm3 outdoors. PM10 outdoor concentrations exhibited a greater spatial variability than the corresponding PM2.5 ones. I/O ratios were close or above 1.00 for PM10 and PM2.5 and smaller than 1.00 for ultrafine particles. Very high I/O ratios were observed when intense activities took place. The initial results of the chemical analysis showed that SO4(-2) accounts for the 6.6 +/- 3.5% of the PM10 and NO3(1) for the 3.1 +/- 1.4%.The corresponding results for PM2.5 are 12.0 +/- 7.7% for SO4(-2) and 3.1 +/- 1.9% for NO3-. PM2.5 SO4(-2) indoor concentrations were highly correlated with outdoor ones and the regression line had the largest slope and a very low intercept, indicative of no indoor sources of fine particulate SO4(-2). The results of the statistical analysis of indoor and outdoor concentration data support the use of SO4(-2) as a proper surrogate for indoor PM of outdoor origin.

Levels of ultrafine particles in different microenvironments--implications to children exposure.

Indoor and outdoor ultrafine particles (UFPs) (0.01 to greater than 1 microm) concentration levels were examined in the area of Athens during cold period of 2003 and 2004. Seven primary schools, located in areas with different characteristics of urbanization and traffic density, as well as a typical suburban residence, were monitored. Moreover, in-vehicle concentration levels, while driving along major avenues and in the heavy-trafficked centre of Athens, were measured (mean route duration: 45 min). UFPs number concentration was monitored by condensation particle counter (model CPC 3007), with a logging time interval of 1 min. The highest mean indoor concentrations were observed in a small carpet-covered library and a teachers' office (8-hour mean equal to 52.6x10(3) particles/cm(3) and 50.2x10(3) particles/cm(3), respectively), at the same school unit. The highest outdoor concentrations (8-hour mean equal to 36.9x10(3) particles/cm(3) and 38.8x10(3) particles/cm(3)) were measured at two schools, both affected by heavy traffic. Finally, the highest in-vehicle concentrations (148.0x10(3)-173.0x10(3) particles/cm(3)) were measured in central commercial areas of Athens during, on average, 55 min drives. Indoor-to-outdoor concentration (I/O) ratios were below 1.00 at all sites. The largest ratio (0.88) was observed in the residence, during a day when there was cleaning activity in the room monitored. Outdoor concentrations diurnal cycles, both outside the schools and the residence, were closely related to traffic. Indoor concentrations inside schools were relatively stable in classrooms. Nevertheless, number concentrations exhibited variability when there were significant changes in room occupancy. Diurnal variation of indoor concentrations at the residence followed the respective outdoor one with a delay of 1 h or less, in the absence of strong indoor sources, indicating the major contribution of outdoor UFPs to the indoor concentration levels. The present work is the first effort to examine UFPs indoor and outdoor concentration levels in the area of Athens. The obtained concentration data give an insight on the concentration levels to which children may be exposed. They may be also very useful in epidemiological studies, in order to estimate children total personal exposure though the calculation of exposures received in different microenvironments. This kind of studies may contribute to the design of effective policies and mitigation measures for the protection of public health.

Source apportionment of PM10 and PM2.5 in major urban Greek agglomerations using a hybrid source-receptor modeling process.

A hybrid source-receptor modeling process was assembled, to apportion and infer source locations of PM10 and PM2.5 in three heavily-impacted urban areas of Greece, during the warm period of 2011, and the cold period of 2012. The assembled process involved application of an advanced computational procedure, the so-called Robotic Chemical Mass Balance (RCMB) model. Source locations were inferred using two well-established probability functions: (a) the Conditional Probability Function (CPF), to correlate the output of RCMB with local wind directional data, and (b) the Potential Source Contribution Function (PSCF), to correlate the output of RCMB with 72h air-mass back-trajectories, arriving at the receptor sites, during sampling. Regarding CPF, a higher-level conditional probability function was defined as well, from the common locus of CPF sectors derived for neighboring receptor sites. With respect to PSCF, a non-parametric bootstrapping method was applied to discriminate the statistically significant values. RCMB modeling showed that resuspended dust is actually one of the main barriers for attaining the European Union (EU) limit values in Mediterranean urban agglomerations, where the drier climate favors build-up. The shift in the energy mix of Greece (caused by the economic recession) was also evidenced, since biomass burning was found to contribute more significantly to the sampling sites belonging to the coldest climatic zone, particularly during the cold period. The CPF analysis showed that short-range transport of anthropogenic emissions from urban traffic to urban background sites was very likely to have occurred, within all the examined urban agglomerations. The PSCF analysis confirmed that long-range transport of primary and/or secondary aerosols may indeed be possible, even from distances over 1000km away from study areas.

Assessment of PM2.5 sources and their corresponding level of uncertainty in a coastal urban area using EPA PMF 5.0 enhanced diagnostics.

Datasets that include only the PM elemental composition and no other important constituents such as ions and OC, should be treated carefully when used for source apportionment. This work is demonstrating how a source apportionment study utilizing PMF 5.0 enhanced diagnostic tools can achieve an improved solution with documented levels of uncertainty for such a dataset. The uncertainty of the solution is rarely reported in source apportionment studies or it is reported partially. Reporting the uncertainty of the solution is very important especially in the case of small datasets. PM2.5 samples collected in Patras during the year 2011 were used. The concentrations of 22 elements (Z=11-33) were determined using PIXE. Source apportionment analysis revealed that PM2.5 emission sources were biomass burning (11%), sea salt (8%), shipping emissions (10%), vehicle emissions (33%), mineral dust (2%) and secondary sulfates (33%) while unaccounted mass was 3%. Although Patras city center is located in a very close proximity to the city's harbor, the contribution of shipping originating emissions was never before quantified. As rotational stability is hard to be achieved when a small dataset is used the rotational stability of the solution was thoroughly evaluated. A number of constraints were applied to the solution in order to reduce rotational ambiguity.

From hygroscopic aerosols to cloud droplets: The HygrA-CD campaign in the Athens basin - An overview.

The international experimental campaign Hygroscopic Aerosols to Cloud Droplets (HygrA-CD), organized in the Greater Athens Area (GAA), Greece from 15 May to 22 June 2014, aimed to study the physico-chemical properties of aerosols and their impact on the formation of clouds in the convective Planetary Boundary Layer (PBL). We found that under continental (W-NW-N) and Etesian (NE) synoptic wind flow and with a deep moist PBL (~2-2.5km height), mixed hygroscopic (anthropogenic, biomass burning and marine) particles arrive over the GAA, and contribute to the formation of convective non-precipitating PBL clouds (of ~16-20µm mean diameter) with vertical extent up to 500m. Under these conditions, high updraft velocities (1-2ms-1) and cloud condensation nuclei (CCN) concentrations (~2000cm-3 at 1% supersaturation), generated clouds with an estimated cloud droplet number of ~600cm-3. Under Saharan wind flow conditions (S-SW) a shallow PBL (<1-1.2km height) develops, leading to much higher CCN concentrations (~3500-5000cm-3 at 1% supersaturation) near the ground; updraft velocities, however, were significantly lower, with an estimated maximum cloud droplet number of ~200cm-3 and without observed significant PBL cloud formation. The largest contribution to cloud droplet number variance is attributed to the updraft velocity variability, followed by variances in aerosol number concentration.

Radioactive pollution in Athens, Greece due to the Fukushima nuclear accident.

As a result of the nuclear accident in Fukushima Dai-ichi power plant, which started on March 11, 2011, radioactive pollutants were transferred by air masses to various regions of the Northern hemisphere, including Europe. Very low concentrations of (131)I, (137)Cs and (134)Cs in airborne particulate matter were measured in Athens, Greece during the period of March 24 to April 28, 2011. The maximum air concentration of (131)I was measured on April 6, 2011 and equaled 490 ± 35 µBq m(-3). The maximum values of the two cesium isotopes were measured on the same day and equaled 180 ± 40 µBq m(-3) for (137)Cs and 160 ± 30 µBq m(-3) for (134)Cs. The average activity ratio of (131)I/(137)Cs in air was 3.0 ± 0.5, while the corresponding ratio of (137)Cs/(134)Cs equaled 1.1 ± 0.3. No artificial radionuclides could be detected in air after April 28, 2011. Traces of (131)I as a result of radioactive deposition were measured in grass, soil, sheep milk and meat. The total deposition of (131)I (dry + wet) was 34 ± 4 Bq m(-2), and of (137)Cs was less than 10 Bq m(-2). The maximum concentration of (131)I in grass was 2.1 ± 0.4 Bg kg(-1), while (134)Cs was not detected. The maximum concentrations of (131)I and (137)Cs in sheep milk were 1.7 ± 0.16 Bq kg(-1) and 0.6 ± 0.12 Bq kg(-1) respectively. Concentrations of (131)I up to 1.3 ± 0.2 Bq kg(-1) were measured in sheep meat. Traces of (131)I were found in a number of soil samples. The radiological impact of the Fukushima nuclear accident in Athens region was practically negligible, especially as compared to that of the Chernobyl accident and also to that of natural radioactivity.