Investigation of naphthalene contamination in olive oil from Greece

Abstract

Incidents of using naphthalene in olive orchards as a repellent of olive fly (Bactrocera oleae) have recently been recorded. Naphthalene, the primary ingredient of mothballs, is described to be diluted in plastic bottles and hanged on the trees releasing its characteristic odor which is supposed to repel olive fly. Since naphthalene has been characterized as possibly carcinogenic to humans and animals, it was considered essential to monitor olive oils regarding their potential contamination with this specific pollutant. To this goal, a simple, sensitive and reliable analytical method for the determination of naphthalene in olive oil has been developed. The method involves extraction with ethyl acetate: acetonitrile (1:1) and determination of naphthalene using gas chromatography triple quadrupole mass spectrometry. The method was validated in four fortification levels, 0.005, 0.01, 0.05, and 0.1?mg/kg in accordance with the EU requirements. The obtained results were acceptable as far as validation criteria are concerned, given recoveries between 71% and 87% and RSDs between 5% and 24%. The limit of determination for naphthalene was set at 0.005?mg/kg based on the lowest concentration level being validated with acceptable accuracy. The analytical technique was successfully applied to 75 olive oil samples collected from oil mills in Greece and no positive results of naphthalene were detected.     

Assessment of the state and management of the cephalopod trawl fishery resources in Greek waters

The cephalopod trawl fishery in Greek waters is reviewed in relation to fishing effort for 1964–1981. The mean annual (1964–81) catch of cephalopods amounted to 1348 tons. Total landings of cephalopods are very well described by the exponential⁹ and linear²⁹ surplus yield models, according to which optimum fishing effort, maximum sustained yield and optimum catch per unit of fishing effort range between 120000–150000HP, 1586–1630 tons and 10–13kgr/HP respectively. In addition, the analysis revealed that cephalopod resources were slightly overfished (according to the linear model) during 1975–1981. Hence, authorities must take immediate measures for the protection and rational management of cephalopod resources in Greek waters. Possible alternative measures are discussed in the text.     

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.     

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.     

Phytoplankton and water quality in a Mediterranean drinking-water reservoir (Marathonas Reservoir, Greece)

Phytoplankton and water quality of Marathonas drinking-water Reservoir were examined for the first time. During the study period (July-September 2007), phytoplankton composition was indicative of eutrophic conditions although phytoplankton biovolume was low (max. 2.7 mm3 l?1). Phytoplankton was dominated by cyanobacteria and diatoms, whereas desmids and dinoflagellates contributed with lower biovolume values. Changing flushing rate in the reservoir (up to 0.7% of reservoir's water volume per day) driven by water withdrawal and occurring in pulses for a period of 15-25 days was associated with phytoplankton dynamics. Under flushing pulses: (1) biovolume was low and (2) both 'good' quality species and the tolerant to flushing 'nuisance' cyanobacterium Microcystis aeruginosa dominated. According to the Water Framework Directive, the metrics of phytoplankton biovolume and cyanobacterial percentage (%) contribution indicated a moderate ecological water quality. In addition, the total biovolume of cyanobacteria as well as the dominance of the known toxin-producing M. aeruginosa in the reservoir's phytoplankton indicated a potential hazard for human health according to the World Health Organization.     

Toxicity and heavy metal contamination of surficial sediments from the Bay of Thessaloniki (Northwestern Aegean Sea) Greece

Surficial sediments (the fraction < 2000 microm) from the Bay of Thessaloniki, in the Northwestern Aegean Sea, Greece were examined for heavy metal and organic carbon contents, as well as for acute LUMIStox toxicity of pore waters (PWs), wet sediment elutriates (WSEs) and dry sediment elutriates (DSEs) obtained from the solid material remaining after PW extraction. WSEs where not toxic. EC20/50 values could be measured in some DSE and PW samples. In all sediment samples, the DSE toxicity was greater than the corresponding PW toxicity. Sediment concentrations of total and labile Cd, Pb, Cu, Cr, Zn, Mn, Ni and Fe were determined and evaluated in relation to sediment quality guidelines. Pollution levels ranged from low to high for certain metals. A misfit between sediment toxicities calculated from heavy metal concentrations and those biologically measured was observed. Toxicity values were in general poorly correlated with sediment's heavy metal or organic carbon content. As significant correlation was however found between the DSE toxicity with total Ni and labile Fe, as well as for the PW toxicity with total Ni, labile Fe and labile Cr.     

Modelling the atmospheric fate and seasonality of polycyclic aromatic hydrocarbons in the UK

This paper presents the results from an exercise in atmospheric contaminant fate modelling, which had three main objectives: (1) to investigate the balance between estimated national atmospheric emissions of six selected PAHs and observed ambient measurements for the UK, as a means of testing the current emission estimates; (2) to investigate the potential influence of seasonally dependent environmental fate processes on the observed seasonality of air concentrations; and (3) after undertaking the first two objectives, to make inferences about the likely magnitude of seasonal differences in sources. When addressing objective 1 with annually averaged emissions data, it appeared that the UK PAH atmospheric emissions inventory was reasonably reliable for fluorene, fluoranthene, pyrene, benzo[a]pyrene and benzo[ghi]perylene--but not so for phenanthrene. However, more detailed analysis of the seasonality in environmental processes which may influence ambient levels, showed that the directions and/or magnitudes of the predicted seasonality did not coincide with field observations. This indicates either that our understanding of the environmental fate and behaviour of PAHs is still limited, and/or that there are uncertainties in the emissions inventories. It is suggested that better quantification of PAH sources is needed. For 3- and 4-ringed compounds, this should focus on those sources which increase with temperature, such as volatilisation from soil, water, vegetation and urban surfaces, and possible microbially-mediated formation mechanisms. The study also suggests that the contributions of inefficient, diffusive combustion processes (e.g. domestic coal/wood burning) may be underestimated as a source of the toxicologically significant higher molecular weight species in the winter. It is concluded that many signatory countries to the UNECE POPs protocol (which requires them to reduce national PAH emissions to 1990 levels) will experience difficulties in demonstrating compliance, because source inventories for 1990 and contemporary situations are clearly subject to major uncertainties.     

An application of parametric and nonparametric models to the assessment of fluoride levels in vegetation exposed to stack emissions of an aluminum reduction plant in Greece

Various statistical models were developed for assessing airborne fluoride (F) levels in natural vegetation near an aluminum reduction plant using as predictor variables the distance from the emission source, the predominating wind, and characteristic topography-geomorphology parameters. Results revealed that F concentrations in vegetation showed a predictable response to both wind conditions and landscape features. The linear model was found to give good estimations, taking advantage of the relatively strong linear correlation between concentration and distance. A nonlinear relationship between the F concentration in vegetation and the other variables was also found, while interactions between the variables were found to be non-first-order. The nonlinear relationship hypothesis was supported by the improved results of various nonlinear models that also indicated the importance of the area's topography-geomorphology and meteorology in model predictions. The application of an artificial neural network (ANN) model showed the closest agreement between predicted and observed values with a correlation coefficient of 0.92. The improved reliability of the ANN and a regression tree model (RTM) also were indicated by the normal distribution of their residuals. The RTM and the ANN were further investigated and found to be capable of identifying the importance of the variables in vegetation exposure to air emissions.     

Navigating uneven terrain: The roles of political skill and LMX differentiation in prediction of work relationship quality and work outcomes

Drawing from social/political influence, leader–member exchange (LMX), and social comparison theories, the present two‐study investigation examines three levels of LMX differentiation (i.e., individual‐level, meso‐level, and group‐level LMX differentiation) and further tests a model of the joint effects of political skill and LMX differentiation on LMX, relative LMX, and employee work outcomes. In Study 1, we used data from 231 employees and found support for the interactive effect of political skill and individual perceptions of LMX differentiation on LMX quality. We also found partial support for the moderating role of individual‐level LMX differentiation on the indirect effects of political skill on self‐rated task performance and job satisfaction via LMX. In Study 2, we used data from 185 supervisor–subordinate dyads and examined both meso‐level and group‐level LMX differentiation via a multilevel moderated mediation model. Results supported the moderating role of group‐level LMX differentiation and group mean LMX on the indirect effects of political skill on supervisor‐rated task performance and contextual performance/citizenship behavior as well as job satisfaction via relative LMX. Overall, the results suggest that politically skilled employees reap the benefits of LMX differentiation, as they enjoy higher absolute LMX and relative (i.e., to their peers) LMX quality. Copyright © 2016 John Wiley & Sons, Ltd.     

On the factors affecting the abundance and distribution of the red bandfish (Cepola macrophthalma) in the Western coast of Greece (Patraikos,Korinthiakos Gulfs and Ionian Sea)

A stepwise multiple linear regression model was used in order to examine the influence of environmental factors on the abundance of the red bandfish (Cepola macrophthalma), a bottom dwelling organism, in the Patraikos and Korinthiakos Gulfs and the Ionian Sea, Western Greece. Samples were collected in June 1985. It was found that 95% of the variation in the abundance of the red bandfish in that area is attributed to the combining negative effect of bottom temperature and salinity and the positive effect of depth. The exact form of the relationship was: log C=449.75–17.12 log T‐110.69 log S + 1.09 log D. The strong influence of these abiotic factors on the abundance of the red bandfish, predicted by the model, is found in concordance with behavioral and ecological information on the red bandfish from the Northeast Atlantic, as well as with data on its distribution in the Greek Seas.