Monitoring of Polycyclic Aromatic Hydrocarbon Levels in Mussels (Mytilus galloprovincialis) from Aquaculture Farms in Central Macedonia Region, Greece, Using Gas Chromatography-Tandem Mass Spectrometry Method.

A new sensitive and selective gas chromatography tandem mass spectrometry (GC-MS/MS) method was developed for the analysis of 26 polycyclic aromatic hydrocarbons (PAHs), including 16 Environmental Protection Agency (EPA) and 15 + 1 European Union (EU) PAHs, in mussel samples from aquaculture farms in Thermaikos and Strymonian Gulf, Central Macedonia Region, in three sampling periods. Concentrations were found at moderate to low values at all sampling sites, without exceeding maximum levels set by EU. Low molecular weight PAHs were predominant in all samples. Seasonal variation of the concentrations was observed; values were slightly higher in the winter period. Use of diagnostic ratios for potential sources of PAHs showed both petrogenic and pyrolitic origin. In comparison to other related studies of mussels from the Mediterranean Sea, Greek mussels cultivated in the studied gulfs are low in contaminants due to minimal environmental pollution effects. Low concentrations of PAHs are in compliance with the low values of other POPs which were found in the mussels.

Heart Failure and PAHs, OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution.

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases' serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 µg L-1). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases' samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes' serum concentrations. PCA-logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning.

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m3, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.

Determination of anabolic androgenic steroids as imidazole carbamate derivatives in human urine using liquid chromatography-tandem mass spectrometry.

Anabolic androgenic steroids are widely abused substances in sports doping. Their detection present limitations regarding the use of soft ion sources such as electrospray or atmospheric pressure chemical ionization by liquid chromatography-tandem mass spectrometry. In the current study, a novel derivatization method was developed for the ionization enhancement of selected anabolic androgenic steroids. The proposed method aims at the introduction of an easily ionizable moiety into the steroid molecule by converting the hydroxyl groups into imidazole carbamates using 1,1'-carbonyldiimidazole as derivatization reagent. The proposed method was applied to water and urine samples spiked with exogenous anabolic androgenic steroids in various concentration levels. Steroid imidazole carbamate derivatives have shown intensive [M+H]+ signals under electrospray ionization and common fragmentation patterns in tandem mass spectrometry mode with [M-CO2 +H]+ and [M-ΙmCO2 +H]+ as major ions with low collision energy. The obtained results showed that the majority of steroids were detectable at concentrations equal or lower to their minimum required performance level according to the World Anti-Doping Agency technical document. The proposed method is sensitive with a preparation procedure that could be easily applied to the analysis of doping control samples.

Polycyclic aromatic hydrocarbons and trace elements dietary intake in inhabitants of Athens, Greece, based on a duplicate portion study.

Concentration levels of 26 polycyclic aromatic hydrocarbons and 20 trace elements were measured in dietary samples, in order to estimate the dietary intake and the potential exposure risk of the Greek population. Dietary samples were collected with the help of 30 volunteers inhabitants of Athens, Greece, according to the duplicate portion study (DPS) method where the determination of the compounds is conducted in the final consumed meal. DPS was selected as an alternative to a total diet study for its feasibility, low cost and realistic image that it provides. PAHs determination was performed by gas chromatography tandem mass spectrometry (GC-MS/MS) and trace elements determination by inductively coupled plasma mass spectrometry (ICP-MS). The estimated mean daily dietary exposure on 26 PAHs for an adult was estimated at 101.47 ng kg-1 body weight day-1, while moderate to low exposure was related to the type and amount of food consumed. Exposure levels to PAHs do not indicate a possible risk for the health of the study group. For toxic, potentially essential and/or essential trace elements the daily exposure calculated for Greek population was in accordance with the reference values of the health-based guidances and compared to previous diet studies reported for the population of other countries was in general similar to the lower bound exposure.

PM2.5-bound organosulfates in two Eastern Mediterranean cities: The dominance of isoprene organosulfates.

PM2.5 samples were collected during 2017-2018 at two Eastern Mediterranean urban sites in Greece, Athens and Patra, in order to study the abundances, the seasonal trends, the sources and the possible impact of gas phase pollutants on organosulfate formation. Each of the studied groups, except that of aromatic organosulfates, presented higher concentrations in Patra compared to those measured in Athens, from 1.1 (nitro-oxy organosulfates) to 3.6 times (isoprene organosulfates). At both sites, isoprene organosulfates was the dominant group which accounted on average for more than 50% of the total measured organosulfates, with the contribution being more than 80% during summer. Strong seasonality was observed at both sites, regarding the isoprene organosulfates, with an almost 21-fold increase from winter to summer. The same pattern, but to a lesser extent, was also observed for monoterpenes organosulfates at both sites. Alkyl organosulfates followed an identical seasonal trend with the highest mean concentrations observed during spring followed by autumn. The seasonality of anthropogenic organosulfates, multisource organosulfates and nitro-oxy organosulfates differed among the two sites or presented a more compound-specific variation. The isoprene-epoxydiol pathway appeared to be the dominant pathway of isoprene transformation, with the compounds iOS211, iOS213 and iOS215 being the major isoprene organosulfate compounds at both sites. Organosulfate contribution to the concentration of particulate matter presented common variation at both sites, ranging from 0.20 ± 0.14% (winter) to 2.5 ± 1.2% (summer) and from 0.21 ± 0.13% (winter) to 5.0 ± 2.5% (summer) for Athens and Patra, respectively. The increased NOx levels in Athens, appeared to affect isoprene organosulfate formation as well as the formation of monoterpene and decalin nitro-oxy organosulfates. Principal component analysis followed by multiple linear regression analysis highlighted the dominance of isoprene organosulfates. In Athens, the possible impact of transportation emissions on the formation of monoterpene nitro-oxy organosulfates is indicated while the correlation of naphthalene organosulfates with low molecular weight polycyclic aromatic hydrocarbons suggests that vehicle emissions may be a significant source. In Patra, the possible contribution of sea on methyl sulfate levels is denoted.

Human serum elements' levels and leukemia: A first pilot study from an adult Greek cohort.

BACKGROUND: The present study focuses on the evaluation of potential relationships between trace elements and acute and chronic types of leukemia, via the determination of their levels in human blood serum. METHODS: A total of 199 serum samples from a Greek cohort were examined, including both leukemia cases and controls. Elements' analysis was carried out using inductively coupled plasma mass spectrometry (ICP-MS) and demographic features such as age, gender, smoking habits and area of residence were recorded and statistically treated applying Shapiro-Wilk, Kolmogorov-Smirnov, Mann Whitney and Kruskal Wallis tests (p < 0.05). Spearman correlation and principal component analysis (PCA) were also performed to investigate possible associations. RESULTS: The results demonstrated significantly higher (p < 0.05) trace elements concentrations in cases' serum compared to that of controls excluding Ba, with Cu (median concentration 1295 µg L-1) being the most abundant in cases. Additionally, concentration of toxic Pb and Cd were found at seven and four fold higher concentrations in cases, respectively. Among the trace elements examined, only Rb (164 µg L-1) was detected in higher concentrations in controls. Ba, Cd and Co presented the lowest concentrations (lower than 1 µg L-1). PCA was performed for overall and classified data, indicating a stronger relation among the toxic As, Cd, Ni and Pb in cases than controls, particularly referring to smokers and industrial sites' residents. Hematological parameters and factors such as age and gender did not present any significant outcome or correlation. CONCLUSIONS: The findings from this pilot study suggest a potential relationship between metals and leukemia, especially concerning the toxic ones. Results from the employed source apportionment tools imply that smoking and atmospheric degradation may be positively related with higher metal serum levels in leukemia patients.

Secondary organic aerosol tracers and related polar organic compounds between urban and rural areas in the Eastern Mediterranean region: source apportionment and the influence of atmospheric oxidants.

Fine particle samples were collected during summer at an urban (LIM) and a rural/background (AGM) site of Cyprus. They were analyzed for pinene and isoprene secondary organic aerosol (PSOA-ISOA) tracers, linear dicarboxylic acids (DCAs), hydroxyacids (HAs), aromatic acids (AAs), monocarboxylic acids (MCAs) and levoglucosan by GC/MS with prior 3-step derivatization. DCAs, AAs, MCAs and levoglucosan exhibited significantly higher concentrations (p < 0.05) in LIM, PSOAs and ISOAs in AGM (p < 0.05), whereas mixed trends were found for HAs. Among DCAs, succinic was the most abundant in both sites, accounting for 42.5% and 36.5% of the total DCAs in LIM and AGM respectively, followed by adipic in LIM (20.1%) and azelaic in AGM (22.4%). Malic, phthalic and palmitic acids were the dominant HA, AA and MCA, respectively. Regarding PSOAs, significant differences were observed between the two sites, with the first-generation products accounting for 59.8% of the total measured PSOAs in AGM, but were remarkably lowered (10.3%) in LIM indicating that they were highly oxidized. 2-Methylerythritol was the dominant ISOA tracer in both sites; nevertheless the elevated relative abundance of 2-methylglyceric acid in LIM implies the influences of higher NOx levels. The increased O3 levels observed in AGM appear to have a significant impact on SOA formation. Source apportionment tools employed revealed factors related to secondary formation processes including oxidation of unsaturated fatty acids, pinene, isoprene and anthropogenic VOCs and factors associated with primary sources such as biomass burning, plant emissions and/or cooking and motor exhaust, with noteworthy differences observed between the two areas.

Trace elements, polycyclic aromatic hydrocarbons, mineral composition, and FT-IR characterization of unrefined sea and rock salts: environmental interactions.

Unrefined sea salt originates from seawater, typically by natural evaporation. Being minimally processed, it contains the natural minerals and impurities of seawater. Despite the wide applications of salt for culinary and food preservation purposes, the available composition data is particularly limited. Since seawater often contains various harmful substances at a trace or ultra-trace level, their determination in unrefined salt is significant in terms of quality control and food safety. Twenty-four (24) samples of unrefined sea and rock salts retailed in Greece were studied in terms of their trace metals and polycyclic aromatic hydrocarbon (PAH) content, which constitute the usual pollutants examined in seawater. In addition, samples' color and mineralogy were recorded and their attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectra were obtained. No statistically significant differences were found between sea and rock salts regarding their trace metal (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) content (excluding V) and the 15 PAHs examined. ATR FT-IR succeeded to discriminate among sea, rock, flower, and underground salty water salts. Compared with the typical trace metal concentrations in seawater, quite high Pb values were determined in both sea and rock salts, whereas outliers in the rest of the trace elements examined were scarce. Median values of the sum of PAH (ΣPAHs) concentrations were calculated equal to 2.1 and 2.6 ng g-1 for sea and rock salts, respectively. Environmental interactions of salt production with trace elements and PAHs are also discussed.

Light vehicle regulated and unregulated emissions from different biodiesels.

In this study, the regulated and unregulated emissions profile and fuel consumption of an automotive diesel and biodiesel blends, prepared from two different biodiesels, were investigated. The biodiesels were a rapeseed methyl ester (RME) and a palm-based methyl ester (PME). The tests were performed on a chassis dynamometer with constant volume sampling (CVS) over the New European Driving Cycle (NEDC) and the non-legislated Athens Driving Cycle (ADC), using a Euro 2 compliant passenger vehicle. The objectives were to evaluate the impact of biodiesel chemical structure on the emissions, as well as the influence of the applied driving cycle on the formation of exhaust emissions and fuel consumption. The results showed that NO(x) emissions were influenced by certain biodiesel properties, such as those of cetane number and iodine number. NO(x) emissions followed a decreasing trend over both cycles, where the most beneficial reduction was obtained with the application of the more saturated biodiesel. PM emissions were decreased with the palm-based biodiesel blends over both cycles, with the exception of the 20% blend which was higher compared to diesel fuel. PME blends led to increases in PM emissions over the ADC. The majority of the biodiesel blends showed a tendency for lower CO and HC emissions. The differences in CO(2) emissions were not statistically significant. Fuel consumption presented an increase with both biodiesels. Total PAH and nitro-PAH emission levels were decreased with the use of biodiesel independently of the source material. Lower molecular weight PAHs were predominant in both gaseous and particulate phases. Both biodiesels had a negative impact on certain carbonyl emissions. Formaldehyde and acetaldehyde were the dominant aldehydes emitted from both fuels.

Identification of thiocyanates by Gas Chromatography - Mass Spectrometry in explosive residues used as a possible marker to indicate black powder usage.

Black Powder (BP) is one of the most common improvised explosives, due to broad access in precursors and simple home-made preparation. Deflagration of black powder results in residues the chemical analysis of which presents limitations and has been performed with several techniques until today; nevertheless, Gas Chromatography-Mass Spectrometry (GC-MS) has never been used. In this study, a simple experimental protocol has been developed towards black powder residues identification, using GC-MS. The sample preparation does not require specialized equipment. Derivatization of thiocyanates coming from BP deflagration and identification of the relative derivative (PBF-SCN) was achieved by monitoring ions m/z 239, 181 and 161. This characteristic derivative was used as a marker to indicate BP usage. The protocol was optimized by investigating individually all experimental parameters and it was evaluated for false positives and negatives. Repeatability and limit of detection were calculated to be %RSD 7.67 and < 1 mg, respectively. No interference coming from other ingredients that might co-exist in BP residues was observed. This protocol may be applied directly and without previous preparation to evidence coming from cases of explosions, thus practically contributing in BP residues identification.

An effective and low cost carbon based clean-up method for PCDD/Fs and PCBs analysis in food.

Sample preparation is of critical importance in dioxin analysis of food and feed samples. It is a complex procedure that includes lipid extraction followed by the application of chromatographic separation techniques, aiming in removing undesirable interferences from the matrix. The separation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from polychlorinated biphenyls (PCBs) is achieved by carbon-based materials which should have high fat capacity in order to be suitable for lipid-containing matrices. Automated methods are available but due to high cost and use of high amounts of solvents, manual methods are also applied. An active carbon material (Carbosphere) with high fat capacity that has been used in the past for manual methods is no longer commercially available. The present study assesses an alternative active carbon material, FU 4652, that can be used for the separation of PCDD/Fs and non-ortho PCBs. Mono-ortho and 6 non-dioxin-like PCBs are also analyzed. The method was validated according to the analytical criteria set in EU regulations 589/2014 and 709/2014. Control samples analyzed for the evaluation of the above material were olive oil reference samples spiked with PCDD/Fs and dioxin-like PCBs at two concentration levels. The new method was tested successfully on food samples of interlaboratory trials organized in previous years. Farmed fish samples collected within national surveillance programs for the years 2016-2017 were analyzed with the method developed. The results obtained indicate that the FU 4652 carbon sorbent has high fat capacity and is capable of separating congeners with good recoveries.

Characterization of PM2.5 chemical composition at the Demokritos suburban station, in Athens Greece. The influence of Saharan dust.

The aim of this work is to study the atmospheric concentrations of selected major and trace elements and ions found in PM2.5, at a suburban site in Athens, Greece, and discuss on the impact of the different sources. Special focus is given to the influence of Saharan dust episodes. The seasonal variability in the metal and ion concentrations is also examined. The results show that PM2.5 mass concentrations are significantly influenced by Saharan dust events; it is observed that when the PM2.5 concentration is higher than 25 µg/m3, five out of six times, the air mass crossed North Africa at an altitude within the boundary layer. Fe is found to be the element with the more significant seasonal variability, displaying much higher concentrations during cold period. The frequent Saharan dust intrusions in the cold period of this dataset may explain this result. Mineral dust and secondary aerosol are the main PM2.5 components (29 and 34%, respectively). During Saharan dust events, the concentration of mineral dust is increased by 35% compared to the days without dust intrusions, while an increase of 68% of the sea salt is also observed. During event days, PM2.5 concentrations are also increased by 14%. Anthropogenic components do not decrease during those days, while sulfate displays even a slight increase, suggesting enrichment of mineral dust with secondary sulfates. The results indicate that African dust intrusions add a rather significant PM pollution load even in the PM2.5 fraction, with implication to population exposure and human health.

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece).

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.

A rapid method for the identification of nitrocellulose in high explosives and smokeless powders using GC-EI-MS.

Nitrocellulose (NC) is one of the most common ingredients in explosive mixtures, however because of its non-volatility, its detection using Gas Chromatography-Electron Ionization-Mass Spectrometry (GC-EI-MS) has not been achieved until today. A rapid method for the identification of NC in bulk explosives using GC-EI-MS was developed. The sample preparation is simple and takes place in a test tube, employing standard equipment of a forensics laboratory. The protocol was optimized and applied to seven, both high and low, commercial explosives, which contained the substance of interest. Moreover, three explosives in the absence of NC were tested to cross check for false positives. Fourteen different standard explosive substances that are usually found in explosive mixtures were then employed in order to monitor the effect of the method on these compounds and check for interferences. Results showed that NC was detected, by its trimethylsilyl (TMS) derivatives, in all the explosive mixtures analyzed and no false positives were observed. The proposed method showed selectivity for NC, as it had no interference coming from other ingredients of explosive mixtures. The protocol introduced offers considerable improvement in identifying the individual components of an explosive mixture and contributes in successful classification of explosives.

Gas/particle partitioning of seven volatile polycyclic aromatic hydrocarbons in a heavy traffic urban area.

Air samples (vapor- and particle-phase) were taken for 19 sampling events during the period from December 1997 to July 1998 in an urban site in the center of Athens. The urban site is densely populated and characterized by heavy traffic circulation and elevated concentrations of VOCs, NO(x), CO and smoke. Seven volatile polycyclic aromatic hydrocarbons (PAHs) were determined in samples. The temperature dependence of gas-phase atmospheric concentration of PAHs, C(g), was investigated using diagrams of natural logarithm of partial pressures (lnP) vs. reciprocal mid-point temperatures. For the six of seven volatile PAHs, the temperature dependence of lnP was statistically significant (at least at the 90% confidence level) and the temperature accounted for 21-67% of the variability in gas-phase concentrations. The gas-phase concentration C(g) of the very volatile PAHs was affected more significantly by changes in temperature, but the variation of the less-volatile PAHs fluoranthene and pyrene C(g), was better explained by changes in temperature. The temperature dependence of gas/particle partitioning constant K(P) was also examined. Regressions of log(K(P))(-1) vs. T(-1) for fluorene, fluoranthene and pyrene were classified into two different temperature ranges. The gas/particle partitioning of PAHs was studied by correlating the partition constant to the sub-cooled liquid saturation vapor pressure (P(L)(o)). The Junge adsorption model underestimated the particle fraction of volatile PAHs probably due to the presence of non-exchangeable fraction. Slopes (m(r)) of the regressions logK(P) vs. logP(L)(o) were different from the value -1 as Pankow's theory predicts. The short distance between the sampling point and the emission sources is also estimated to be a factor that causes deviations from the theoretical value. Evidence that atmospheric conditions favorable for secondary aerosol formation coincide with higher value of m(r), was provided by limited sampling events. An interrelation was found to exist between the m(r) values, allowing the prediction of the gas/particle partitioning of a series of seven PAHs by the measurement of a single PAH partitioning.

Carbonyl compounds in the urban environment of Athens, Greece.

The concentration levels of 15 selected carbonyl compounds in 62 samples were determined at two sites in Athens basin from June to December 2000. Formaldehyde was the most abundant species (0.05-39 microg m(-3)), which comprised from 22% to 37% of the total measured compounds, followed by acetaldehyde (4.32-49 microg m(-3)), acetone/acrolein (0.64-198 microg m(-3)) and butanal (0.79-140 microg m(-3)). The mean formaldehyde/acetaldehyde and acetaldehyde/propanal molar ratios were calculated. No significant seasonal differences were observed for all the carbonyls. Photochemical production was found to weigh upon atmospheric levels for 83-93% in summer days, dropping below 33% in the winter. The importance of formaldehyde and acetaldehyde as a source of hydroxyl radicals in Athens was also assessed.

Characterization of lead, cadmium, arsenic and nickel in PM(2.5) particles in the Athens atmosphere, Greece.

Concentrations of Pb, Cd, As and Ni in PM(2.5) particles were measured in samples collected, using low volume PM(2.5) samplers (Harvard Impactor system, HI) at two sites in Athens basin; Patission Street in Athens city center and Rentis, a semi-urban and industrial area, during March 1995-March 1996. Sample analysis for Pb, Cd, Ni and As was accomplished by electrothermal atomic absorption spectrometry after total digestion. Annual geometric mean values in 183 PM(2.5) particles samples were found to be: Pb: 143 nanogram(-3); Cd: 0.34 nanogram(-3); Ni: 4.55 nanogram(-3); As: 0.79 nanogram(-3). The geographical and temporal distribution patterns were investigated. Pb exhibited higher values during the winter period. For the other elements no significant seasonal variation was observed. Wind direction, air temperature and relative humidity affected element concentrations. Principal component analysis was applied on the data to enable source apportionment of toxic elements in PM(2.5) particles. It was found that Pb, As and Ni have common sources, which could be vehicles emissions/oil combustion and resuspended road dust. Cd and a portion of As originate from industrial activities.

Dispersion of volatile hydrocarbons in urban street canyons.

Volatile hydrocarbons (VHCs) were monitored in two urban street canyons for 16 days. Measurements of 15 selected VHCs were performed simultaneously at three different sampling heights: at street level (2 m), at 8 m, and at the rooftop (25 m above the ground). The aim of the study was to investigate the factors responsible for the horizontal and vertical changes in VHC concentrations. Physical parameters controlling the concentration gradients (wind flow and speed) were enabled. It was concluded that dilution and dispersion decrease the concentrations of HCs emitted at street level by approximately a factor of 6 between rooftop and street levels. Low winds and winds parallel to the street axis were identified as the worst dispersion conditions. The correlation between the measured VHC concentrations gave an insight into their fate. An empirical relationship between CO and benzene was established. These results may have important implications in planning monitoring studies to support research on population exposure in urban areas.

Volatile hydrocarbons in the atmosphere of Athens, Greece.

This work presents the results of one-year monitoring study of Volatile Hydrocarbons, VHCs, in the atmosphere of Athens. It is the first systematic attempt to determine the VHC levels in the Athens' atmosphere with the very well known photochemical pollution problems. The purpose of this work was to create a database concerning VHCs in order to evaluate the photochemical pollution in this area (ozone creation, case studies and meteorology). Totally, 308 samples were collected at three different sites used in the state-monitoring programme involving the criteria pollutants. Air samples were collected on Tenax TA tubes and analysed by thermal desorption and dual column GC dual FID. Fifteen selected compounds were studied; 6 alkanes and 9 benzenoid compounds. The measured values of individual alkanes ranged from 0.39 pg m(-3) to 33 pg m(-3), and those of aromatics from 0.20 pg m(-3) to 616 pg m(-3). The sum of all 15 VHC concentrations ranged between 16 and 1697 pg m(-3). The time and spatial variations in the concentration of these compounds were assessed. Volatile hydrocarbons exhibited a clear seasonal and time cycle, showing higher concentrations during winter and early morning hours. Study of the spatial variations of VHC levels showed higher concentrations at the center of the city. The variation of toluene/benzene ratio and the correlation between VHCs, criteria pollutants (CO, NOx and O3) and meteorological parameters were also assessed. It was demonstrated that a trip-line of the VHCs concentration at the city center doubles the ozone concentration at peripheral areas under favourable meteorological conditions.