Ionic composition of PM2.5 at urban sites of northern Greece: secondary inorganic aerosol formation

This study investigates the water-soluble ionic constituents (Na⁺, K⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Cl^?, NO₃ ^?, SO₄ ^2?) associated to PM_2.5 particle fraction at two urban sites in the city of Thessaloniki, northern Greece, an urban traffic site (UT) and urban background site (UB). Ionic constituents represent a significant fraction of PM_2.5 mass (29.6 at UT and 41.5 % at UB). The contribution of marine aerosol was low (<1.5 %). Secondary inorganic aerosols (SIA) represent a significant fraction of PM_2.5 mass contributing to 26.9?±?12.4 % and 39.2?±?13.2 % at UT and UB sites, respectively. Nitrate and sulfate are fully neutralized by ammonium under the existing conditions. The ionic constituents were evaluated in relation to their spatial and temporal variation, their gaseous precursors, meteorological conditions, local and long-range transport.     

Local deposition of mercury in topsoils around coal-fired power plants: is it always true?

Mercury (Hg) is a toxic element that is emitted to the atmosphere through human activities, mainly fossil fuel combustion. Hg accumulations in soil are associated with atmospheric deposition, while coal-burning power plants remain the most important source of anthropogenic mercury emissions. In this study, we analyzed the Hg concentration in the topsoil of the Kozani–Ptolemais basin where four coal-fired power plants (4,065 MW) run to provide 50 % of electricity in Greece. The study aimed to investigate the extent of soil contamination by Hg using geostatistical techniques to evaluate the presumed Hg enrichment around the four power plants. Hg variability in agricultural soils was evaluated using 276 soil samples from 92 locations covering an area of 1,000 km². We were surprised to find a low Hg content in soil (range 1–59 μg kg^?1) and 50 % of samples with a concentration lower than 6 μg kg^?1. The influence of mercury emissions from the four coal-fired power plants on soil was poor or virtually nil. We associate this effect with low Hg contents in the coal (1.5–24.5 μg kg^?1) used in the combustion of these power plants (one of the most Hg-poor in the world). Despite anthropic activity in the area, we conclude that Hg content in the agricultural soils of the Kozani–Ptolemais basin is present in low concentrations.     

The fate of lindane in the conventional activated sludge treatment process

A pilot-scale treatability study was performed to evaluate the fate of lindane (gamma-hexachlorocyclohexane) in wastewater treatment plants operating in the conventional activated sludge mode. Different types of wastewater (industrial and municipal) spiked with variable lindane concentrations were used at different dosing rates in order to determine distribution and removal under various operational conditions. The major amount (67-91%) of lindane inputs to the treatment process was found to concentrate in primary sludge. A significant linear correlation between the compound's partition coefficient (logKp) and the organic fraction of primary sludge (foc) was found. Sorption on primary sludge solids was concluded to be the major removal mechanism. Only 0.1-2.8% of lindane inputs was concentrated in activated sludge. Lindane losses in primary treatment were low (4-26%). Higher losses (up to 61%) were observed during the biological treatment probably due to biodegradation. These losses were negatively correlated with the inflow rate of lindane into the aeration tank. Activated sludge aged about 23 d presented the maximum loss of lindane. Increased sludge age was associated with increased percentages of lindane in the final effluent.     

Removal of pesticides from surface waters by combined physicochemical processes. Part I: Dodine

The simultaneous action of powdered activated carbon and several coagulant agents on the removal of the fungicide dodine from spiked distilled water, was studied. As coagulants, ferric chloride (FeCl₃) and basic polyaluminium chlorosulfate ([Al(OH)_xCl_y(SO₄)_z]_n) were examined, using polyacrylamide, in certain cases, as coagulant aid (polyelectrolyte). The efficiency of dodine removal was investigated with respect to the added amount of powdered activated carbon (PAC), the pH value, as well as the type and dose of coagulant and polyelectrolyte. The experiments were performed applying the standard jar-test procedure. The initial concentration of dodine was 250 μg/L. At this concentration and pH range 5–8 it was found that a dose of 100 mg/L PAC was necessary to achieve more than 98% removal of dodine, whereas lower removal (91–93%) was obtained applying half the dose of PAC under the same conditions. However, when 10–100 mg/L FeCl₃ were simultaneously added with PAC, the removal efficiency increased to >98%, even with the half PAC dose.     

PCDD/Fs and PCBs in airborne particulate matter of the greater Thessaloniki area, N. Greece

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.     

Levels of total suspended particulate matter and major trace elements in Kosovo: a source identification and apportionment study

Concentration levels of total suspended particles (TSP) and 27 major, minor and trace elemental components were determined at four sites in Kosovo through a 1-year survey (January-December 2002). Ambient concentrations were evaluated in comparison to limit values. The origin of elemental TSP constituents was investigated by calculating enrichment factors and diagnostic ratios. Multivariate statistics, such as hierarchical cluster analysis and factor analysis, were also employed to identify emission sources. A multivariate statistical receptor model (Absolute Principal Component Analysis, APCA) was applied to quantify source contributions. Soil dust, cement production, vehicular emissions, brake wear, and fuel combustion were identified as major sources with variable contributions at the four sampling sites.     

Chemical composition and mass closure of ambient coarse particles at traffic and urban-background sites in Thessaloniki,Greece

Concentrations and chemical composition of the coarse particle fraction (PM_c) were investigated at two urban sites in the city of Thessaloniki, Greece, through concurrent sampling of PM₁₀ and PM_2.5 during the warm and the cold months of the year. PM_c levels at the urban-traffic site (UT) were among the highest found in literature worldwide exhibiting higher values in the cold period. PM_c levels at the urban-background site (UB) were significantly lower exhibiting a reverse seasonal trend. Concentration levels of minerals and most trace metals were also higher at the UT site suggesting a stronger impact from traffic-related sources (road dust resuspension, brake and tire abrasion, road wear). According to the chemical mass closure obtained, minerals (oxides of Si, Al, Ca, Mg, Fe, Ti, and K) dominated the PM_c profile, regardless of the site and the period, with organic matter and secondary inorganic aerosols (mainly nitrate) also contributing considerably to the PM_c mass, particularly in the warm period. The influence of wind speed to dilution and/or resuspension of coarse particles was investigated. The source of origin of coarse particles was also investigated using surface wind data and atmospheric back-trajectory modeling. Finally, the contribution of resuspension to PM_c levels was estimated for air quality management perspectives.     

Concentrations and source apportionment of PM10 and associated elemental and ionic species in a lignite-burning power generation area of southern Greece

Ambient concentrations of PM₁₀ and associated elemental and ionic species were measured over the cold and the warm months of 2010 at an urban and two rural sites located in the lignite-fired power generation area of Megalopolis in Peloponnese, southern Greece. The PM₁₀ concentrations at the urban site (44.2?±?33.6 μg m^?3) were significantly higher than those at the rural sites (23.7?±?20.4 and 22.7?±?26.9 μg m^?3). Source apportionment of PM₁₀ and associated components was accomplished by an advanced computational procedure, the robotic chemical mass balance model (RCMB), using chemical profiles for a variety of local fugitive dust sources (power plant fly ash, flue gas desulfurization wet ash, feeding lignite, infertile material from the opencast mines, paved and unpaved road dusts, soil), which were resuspended and sampled through a PM₁₀ inlet onto filters and then chemically analyzed, as well as of other common sources such as vehicular traffic, residential oil combustion, biomass burning, uncontrolled waste burning, marine aerosol, and secondary aerosol formation. Geological dusts (road/soil dust) were found to be major PM₁₀ contributors in both the cold and warm periods of the year, with average annual contribution of 32.6 % at the urban site vs. 22.0 and 29.0 % at the rural sites. Secondary aerosol also appeared to be a significant source, contributing 22.1 % at the urban site in comparison to 30.6 and 28.7 % at the rural sites. At all sites, the contribution of biomass burning was most significant in winter (28.2 % at the urban site vs. 14.6 and 24.6 % at the rural sites), whereas vehicular exhaust contribution appeared to be important mostly in the summer (21.9 % at the urban site vs. 11.5 and 10.5 % at the rural sites). The highest contribution of fly ash (33.2 %) was found at the rural site located to the north of the power plants during wintertime, when winds are favorable. In the warm period, the highest contribution of fly ash was found at the rural site located to the south of the power plants, although it was less important (7.2 %). Moderate contributions of fly ash were found at the urban site (5.4 and 2.7 % in the cold and the warm period, respectively). Finally, the mine field was identified as a minor PM₁₀ source, occasionally contributing with lignite dust and/or deposited wet ash dust under dry summer conditions, with the summertime contributions ranging between 3.1 and 11.0 % among the three sites. The non-parametric bootstrapped potential source contribution function analysis was further applied to localize the regions of sources apportioned by the RCMB. For the majority of sources, source regions appeared as being located within short distances from the sampling sites (within the Peloponnesse Peninsula). More distant Greek areas of the NNE sector also appeared to be source regions for traffic emissions and secondary calcium sulfate dust.     

The fate of dissolved organic carbon (DOC) in the wastewater treatment process and its importance in the removal of wastewater contaminants

Goal, Scope and Background Dissolved organic carbon (DOC) constitutes a parameter of organic pollution for waters and wastewaters, which is not so often studied, and it is not yet regulated by directives. The term ‘DOC’ is used for the fraction of organics that pass through a 0.45 μm pores’ size membrane. The type of wastewater plays an important role in the quality of DOC and it has been shown that DOC may contain aquatic humic substances, hydrophobic bases, hydrophobic neutrals, hydrophilic acids, hydrophilic bases and hydrophilic neutrals. The quality of the DOC is expected to affect its fate in a wastewater treatment plant (WWTP), since a considerable fraction of DOC is not biodegradable, and it may be released in the aquatic environment together with the treated effluent. In the present study, the occurrence of DOC during the wastewater treatment process is investigated and its removal rates during primary, secondary and overall treatment are being estimated. Furthermore, a correlation is being attempted between DOC and the concentrations of selected Persistent Organic Pollutants (POPs) and Heavy Metals (HMs) in the dissolved phase of wastewaters, to examine whether there are common sources for these pollution parameters in WWTPs. Also, DOC is being correlated with the partition coefficients of the above-mentioned pollutants in wastewater, in order to examine the effect of ‘solubility enhancement’ in WWTPs and to evaluate the result of this phenomenon in the efficiency of a WWTP to remove organic pollutants. Methods For the purposes of this study, 24-h composite wastewater samples were collected from the influent (raw wastewater, RW), the effluent of primary sedimentation tank (primary sedimentation effluent, PSE) and the effluent of secondary sedimentation tank (secondary sedimentation effluent, SSE). Samples were analyzed for the presence of 26 POPs (7 PCBs and 19 organochlorine pesticides), 8 HMs and DOC. Results and Discussion Mean concentrations of DOC in RW and PSE were at similar levels (∼ 70 mg l⁻¹), suggesting that primary treatment has a minor effect on the DOC content of wastewater. DOC concentrations in SSE were significantly lower (∼ 19 mg l⁻¹) as a result of the degradation of organic compounds in the biological reactor. Calculated removals of DOC were 0.8% in the primary treatment, 63% in the secondary treatment, and 69% in the overall treatment, exhibiting large differences from other organic pollution parameters, such as BOD and COD. The overall DOC removal was found to be independent from the DOC concentration in raw wastewater. Poor correlation was also observed between the DOC content and the concentrations of wastewater contaminants, such as persistent organic pollutants (POPs) and heavy metals (HMs), probably suggesting that their occurrence in WWTPs is due to different sources. A good negative linear relationship was revealed between DOC concentrations and the logarithms of the distribution coefficients (K _d) of various POPs and HMs between the solid and the liquid phases of wastewater. This relationship suggests that DOC facilitates hydrophobic pollutants to remain in the dissolved phase thus causing lower removal percentages during the treatment process. Conclusion DOC was measured at three stages of a municipal WWTP that receives mainly domestic wastewater and urban runoff. DOC concentrations in untreated and primarily treated wastewater were almost equal, and only after the secondary sedimentation there was a decrease. Concentrations and removal rates of DOC were in the same levels as in other WWTPs that receive municipal wastewater. The origin of DOC was found to be different to the one of POPs and of HMs, as no correlation was observed between the concentrations of DOC and the concentrations of these pollutants. On the contrary, DOC was found to have significant negative correlation with the K _d of all pollutants examined, suggesting that it plays an important role in the partitioning of those pollutants between the dissolved and the sorbed phase of wastewaters. This effect of DOC on partitioning can affect the ability of WWTPs to remove toxic pollutants, and that way it facilitates the discharge of those chemicals in the aquatic ecosystems together with the treated effluent. Recommendation By the results of this work it is shown that the presence of DOC in wastewaters can significantly affect the partition of hazardous pollutants between the dissolved and the sorbed phase. It is therefore of importance that this parameter is controlled more in wastewaters, since it can cause a decrease in the efficiency of WWTPs to remove quantitatively persistent pollutants.     

Seasonal variation of the size distribution of urban particulate matter and associated organic pollutants in the ambient air

Size-segregated samples of urban particulate matter (<0.95, 0.95–1.5, 1.5–3.0, 3.0–7.5, >7.5 μm) were collected in Thessaloniki, northern Greece, during winter and summer of 2007–2008, in order to study the size distribution of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs) including n-alkanes and the isoprenoids pristane and phytane, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). All organic compounds were accumulated in the particle size fraction <0.95 μm particularly in the cold season. Particulate matter displayed a bimodal normalized distribution in both seasons with a stable coarse mode located at 3.0–7.5 μm and a fine mode shifting from 0.95–1.5 μm in winter to <0.95 μm in summer. Unimodal normalized distributions, predominant at 0.95–1.5 μm size range, were found for most organic compounds in both seasons, suggesting gas-to-particle transformation after emission. A second minor mode at larger particles (3.0–7.5 μm) was observed for C₁₉ and certain OCPs suggesting redistribution due to volatilization and condensation.