Study on particulate matter air pollution,source origin,and human health risk based of PM10 metal content in Volos City,Greece

Investigations on the fluctuation in PM₁₀ air pollution in Volos, a medium-sized industrialized port city in the Mediterranean, are presented for the 5-year period between 2009 and 2014. The levels detected have been examined in relation to legislatively set limits, sampling year, and day of the week. A PM₁₀ spring sampling campaign has been performed in 2014 and metals and other elements in the PM₁₀ mass have been quantified. Source origin has been attempted for the latter sampling campaign and human health risk has been assessed. Results show compliance with the mean annual value of 40 μg m^?3 of 2008/50/EC for the city; however, exceedances of the daily quality standard of 50 μg m^?3 were frequently recorded. Shifts in PM₁₀ concentrations and in contributing sources have been recorded; nevertheless, longer duration data series are needed for safe deductions. Element measurements have enabled source identification for early summer of 2014, with Earth's crust minerals and anthropogenic sources being the main factors. Cumulative non-carcinogenic risk may exceed the threshold value of 1. Possible involvement of sea salt aerosol and desert dust long-range transport has also been assessed. These results may furnish databases on PM pollution of Greek cities as well as other Mediterranean urban centers with similar characteristics.     

Assessing PM10 source reduction in urban agglomerations for air quality compliance

The objective of this work was to study PM(10) and PM(2.5) concentration data available from monitoring stations in two large urban agglomerations in Greece and to estimate the emissions reduction required for compliance with the EU Air Quality Standards (AQS) for particulate matter. The cities studied are namely the Athens and Thessaloniki Metropolitan Areas (AMA and TMA, respectively). PM(10) concentrations during the period 2001-2010 have been evaluated for 15 air quality monitoring stations in the two urban areas. It was found that the concentrations of PM(10) during the period studied constantly exceeded the threshold values at the traffic and industrial stations in TMA and most of the traffic sites in AMA. Most of the occurrences of non-attainment to the daily AQSs were observed during the winter period at all stations (more pronounced for TMA stations). The reduction in current emission source strength to meet the air quality goal was calculated by the rollback equation using PM(10) day-averaged concentrations over the selected period at each station. Among the lognormal and Weibull distributions, the lognormal distribution was found to best fit the frequency distributions of PM(10) concentrations at the selected stations. The results showed that the minimum reduction required in order to meet the AQS in the AMA ranges from approximately 20 to 38% and up to 11% for traffic and background stations, respectively. Reductions in the range of 31% for traffic and 44% for industrial areas in TMA are also required. The same methodology was applied to PM(2.5) concentrations in the AMA and showed that emission reductions up to 31% are necessary in order to meet the 2020 EU AQS. Finally, continuous concentration data of organic (OC) and elementary carbon (EC) in PM(2.5) were used to study the possibility of achieving specific emission attenuation objectives in AMA.     

Cesium-137 monitoring using mosses from W. Macedonia,N. Greece

¹³⁷Cs activities in mosses and substrate (soil, bark) collected from W. Macedonia, Greece were measured 20 years after the Chernobyl reactor accident. Archive material from previous studies was also used for comparison and diachronic estimation of the radio-contamination status. A gradual decrease was detected which depended on various factors such as the collected species, location, growth rate and substrate. Maximum accumulation capacity of ¹³⁷Cs was observed in the epilithic mosses in comparison to the epiphytic ones. The ¹³⁷Cs content in the bark of the two broad-leaved species (oak and fagus) was higher than that of the conifer (pinus). Bark specimens of about 50 cm height were in general more contaminated than those of 200 cm. Autoradiography revealed an amount of ¹³⁷Cs distributed more or less uniformly in moss thalli. The high ¹³⁷Cs activities found in mosses 20 years after Chernobyl suggest that these primitive plants are effective, suitable and inexpensive biological detectors of the distribution and burden of radionuclide fallout pattern.     

Do lagoons near concentrated animal feeding operations promote nitrous oxide supersaturation?

Animal wastewater lagoons nearby concentrated animal feeding operations (CAFOs) represent the latest tendency in global animal farming, severely impacting the magnitude of greenhouse gas emissions, including nitrous oxide (N₂O). We hypothesized that lagoon wastewater could be supersaturated with N₂O as part of incomplete microbial nitrification/denitrification processes, thereby regulating the N₂O partitioning in the gaseous phase. The objectives of this study were: (i) to investigate the magnitude of dissolved N₂O concentrations in the lagoon; and (ii) to determine the extent to which supersaturation of N₂O occurs in wastewater lagoons. Dissolved N₂O concentrations in the wastewater samples were high, ranging from 0.4 to 40.5 μg N₂O mL⁻¹. Calculated dissolved N₂O concentrations from the experimentally measured partition coefficients were much greater than those typically expected in aquatic systems (<∼0.6 μg N₂O mL⁻¹). Knowledge of the factors controlling the magnitude of N₂O supersaturation could potentially bridge mass balance differences between in situ measurements and global N₂O models.     

Nitrous oxide supersaturation at the liquid/air interface of animal waste

Concentrated animal feeding operations around the globe generate large amounts of nitrous oxide (N₂O) in the surrounding atmosphere. Liquid animal waste systems have received little attention with respect to N₂O emissions. We hypothesized that the solution chemistry of animal waste aqueous suspensions would promote conditions that lead to N₂O supersaturation at the liquid/air interface. The concentration of dissolved N₂O in poultry litter (PL) aqueous suspensions at 25 °C was 0.36 μg N₂O mL⁻¹, at least an order of magnitude greater than that measured in water in equilibrium with ambient air, suggesting N₂O supersaturation. There was a nonlinear increase in the N₂O Henry constants of PL from 2810 atm/mole fraction at 35 °C to 17 300 atm/mole fraction at 41 °C. The extremely high N₂O Henry constants were partially ascribed to N₂O complexation with aromatic moieties. Complexed N₂O structures were unstable at temperatures > 35 °C, supplying the headspace with additional free N₂O concentrations.     

Using Various Guidelines and Approaches for the Assessment of Marine Sediment Quality

The aim of the present study is to explore the implications of using different quality guidelines and approaches for marine sediment characterization. As a case study, the sediments of Souda Port, Crete, Greece, were examined in order to assess heavy metal contamination and to estimate anthropogenic contribution and potential adverse effects to aquatic environment, as well as to indicate feasible future management options. The concentration of six heavy metals (Co, Cr, Cu, Ni, Pb, and Zn) was determined and compared with different sediment quality guidelines (SQGs) and regional/national criteria established for dredged material characterization and management. In addition, the geo-accumulation index (I_geo) was calculated and the sediments toxicity and heavy metals bioavailability were determined. Based on the experimental data, it is deduced that Souda sediments are characterized as moderately polluted only in terms of Co, Ni, and Pb.     

Part II: temporal and spatial distribution of multiclass pesticide residues in lake sediments of northern Greece: application of an optimized MAE-LC-MS/MS pretreatment and analytical method

The development and application of an analytical methodology for the pretreatment and determination of 253 multiclass pesticides, in lake sediment samples, using liquid chromatography coupled with mass spectrometry (LC-MS/MS) are described in this work. Sediments of lakes Volvi, Doirani, and Kerkini, located in northern Greece, were collected in two-time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methodology. Microwave-assisted extraction (MAE) was applied to extract the pesticide residues from lake sediment samples. Analytical results were stored, categorized, and visualized using geographical information systems, in order to assess and observe spatial and temporal variations of the pollution. Main pesticides that were detected included the following: amitrole, tebuconazole, phoxim, diniconazole, sethoxydim, temephos, tetrachlorvinphos, pendimethalin, boscalid, disulfoton sulfone, lenacil, propiconazole, cycloxydim, pyridaben, and terbuthylazine. Amitrole, diniconazole, and tebuconazole were found to be common in all three lakes. Lakes Kerkini and Doirani exhibited increased concentrations during the first sampling period (winter 2010) with predominant pesticide classes, triazines/triazoles and organophosphates. Pollution is mainly located near the populated villages of the lakes and the nearby cultivations. During the second sampling period, pesticide concentrations appear lower and located in sediments near the center of the lake. Lake Volvi exhibits increased pesticide concentrations during the second sampling period, temporal and spatial variations and different pesticide profile pattern. Increased pollution occurs near the center of the lake during the first sampling period, mainly comprised by triazines/triazoles and organophosphates. During the second sampling period, the majority of the sediment samples demonstrated a different pesticide profile dominated by unclassified pesticides and triazines/triazoles. Mineralogical analysis of the samples demonstrates that sediments are mainly composed of clay, mud, and sand particles, and they present spatial variations. Near the center of the lakes, sediments appear to be more fine-grained with higher clay content and are more likely to adsorb pesticides.     

Controlling the fate of roxarsone and inorganic arsenic in poultry litter

A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.     

Comparison and analysis of different approaches for estimating the human exposure to phthalate esters

The human exposure estimates for dibutyl (DBP) and bis(2-ethylhexyl) phthalate (DEHP) made by two models EUSES and ACC-Human, and by an estimation approach which utilized measured concentrations in exposure media, were compared. The approach which utilized the latest monitoring data for important exposure media, yielded median daily intakes for adult humans for DBP and DEHP of 2.7 and 5.6 microg/kg body weight per day, respectively, which were in the same range as previous estimates based on back-calculation from urinary metabolites. EUSES estimated average daily intakes of DBP and DEHP for humans that were between 8 and 13 times lower. ACC-Human does not estimate average daily intakes, but ACC-Human-estimated human milk concentrations/fugacities were more than a thousand times lower than measured concentrations/fugacities in human milk. It was concluded that the two models underestimate human exposure to phthalate esters because they consider only a few key pathways that are known to be important for other, more persistent, hydrophobic organic compounds. Further, it was shown that there are differences between the two models on the methodology for estimating concentrations in exposure media such as vegetation, milk, beef and fish. ACC-Human uses a mechanistic approach for estimating transfer through aquatic and terrestrial food chains that are known to be important for human exposure to persistent, hydrophobic organics and can, unlike EUSES, account for food chain metabolism. It proved difficult, however, to obtain organism metabolism rates needed as model inputs to ACC-Human. If exposure estimates of phthalate esters are needed, it is recommended to use an estimation approach based on high quality monitoring data as presented here and/or back-calculate daily intake from concentrations of metabolites in human urine samples from the general population.