PM10-bound polycyclic aromatic hydrocarbons (PAHs) in the Greater Area of Athens, Greece

Polycyclic aromatic hydrocarbons (PAHs) associated to ambient PM10 were determined at four sites within the Greater Athens Area (GAA), Greece, during the period May 2001-June 2002. Daily average PM10 samples were collected using reference samplers installed in two urban locations (Maroussi, MAR and Aristotelous, ARI), a mixed urban-industrial location (Elefsina, ELE), and a background location (Thracomacedones, THR). Spatial and temporal variation of ambient PAH levels and possible relationships with conventional air pollutants and meteorological parameters were investigated. Moreover, source identification was attempted using diagnostic ratios. The PAH concentrations observed in this study, even in downtown Athens, were towards the lowest end of the range of values reported for other European urban locations. The mean concentration of the well known carcinogen B[alpha]Py was at all four sites below the proposed value of 1 ng m-3 (annual average assessment threshold). Automobile traffic was identified as the major PAH source in the GAA exhibiting greatest contribution in the urban sites.     

The evaluation of electrical energy per order (E(Eo)) for photooxidative decolorization of four textile dye solutions by the kinetic model

Photooxidative decolorization of four textile dyestuffs, C.I. Acid Orange 7 (AO7), C.I. Acid Orange 8 (AO8), C.I. Acid Orange 52 (AO52) and C.I. Acid Blue 74 (AB74), by UV/H2O2 was investigated in a laboratory scale photoreactor equipped with a 15 W low pressure mercury vapour lamp. The decolorization of the dyes was found to follow pseudo-first-order kinetics, and hence the figure-of-merit electrical energy per order (E(Eo)) is appropriate for estimating the electrical energy efficiency. The E(Eo) values were found to depend on the concentration of H2O2, concentration and basic structure of the dye. This study shows that these textile dyes can be treated easily and effectively with the UV/H2O2 process with E(Eo) values between 0.4 and 5 kW h m-3 order-1, depending on the initial concentrations of dyes and H2O2. The kinetic model, based on the initial rates of degradation, provided good prediction of the E(Eo) values for a variety of conditions.     

Bioavailability of contaminants estimated from uptake rates into soil invertebrates

It is often argued that the concentration of a pollutant inside an organism is a good indicator of its bioavailability, however, we show that the rate of uptake, not the concentration itself, is the superior predictor. In a study on zinc accumulation and toxicity to isopods (Porcellio scaber) the dietary EC(50) for the effect on body growth was rather constant and reproducible, while the internal EC(50) varied depending on the accumulation history of the animals. From the data a critical value for zinc accumulation in P. scaber was estimated as 53 microg/g/wk. We review toxicokinetic models applicable to time-series measurements of concentrations in invertebrates. The initial slope of the uptake curve is proposed as an indicator of bioavailability. To apply the dynamic concept of bioavailability in risk assessment, a set of representative organisms should be chosen and standardized protocols developed for exposure assays by which suspect soils can be evaluated.     

Formation of PCDD/Fs in the sintering process: role of the grid-Cr2O3 catalyst in the de novo synthesis

The sintering process is among the major sources of the very toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the environment. At the industrial scale, it has been shown that dust collected on the grid, which supports the feed, contains PCDD/Fs amounts between the values found in the bottom of the cake and the values found on dust collected during gas sampling in the wind boxes. This fact suggests that the grid, containing 25wt.% of chromium, could have a catalytic activity in PCDD/Fs formation during the sintering process. This research tries to study this potential role. The de novo synthesis of PCDD/Fs is simulated at laboratory scale by thermal treatments of samples mixed with grid filings or Cr2O3. The thermal experiments performed with E.S.P. dust (dust collected in the electrostatic precipitator of a sintering plant) or graphite mixed with grid filings do not allow to confirm a role of the grid in PCDD/Fs formation during the industrial process. On the other hand, it has been shown that Cr2O3 can be considered as a catalyst in the de novo synthesis of PCDD/Fs. This compound takes place in the two steps of the de novo synthesis: the degradation of the carbon matrix as well as the chlorination reactions.     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.     

Enhancing bioremediation of diesel oil and gasoline in soil amended with an agroindustry sludge

This paper presents a study of the bioremediation of diesel oil and gasoline by a series of controlled laboratory tests. Sludge from an agroindustry was used to enhance bioremediation of both gasoline and diesel oil mixed with a soil mass to compare its efficiency with that of a mineral fertilizer. Effects of soil microbiology and soil mixtures were investigated by means of evolution of CO2, microorganism populations at 90 days, pH at 65 and 95 days, mineral nitrogen, and gas chromatographic analysis of the benzene, toluene, methyl tertiary butyl ether, C8, and C9+total aromatics at the end of the experiments. Treatments containing sludge showed better soil conditions after 170 days of treatment (inorganic nitrogen and microbiota activity) compared with gasoline and diesel oil without amendments. Samples had no detectable traces of the measured hydrocarbons at 170 days of treatment.     

Monitoring and toxicity of sulfonated derivatives of benzene and naphthalene in municipal sewage treatment plants

Monitoring benzenesulfonates (BS) and naphthalenesulfonates (NS) took place in five municipal sewage treatment plants (STP). A previously optimized method based on solid phase extraction with polymeric cartridges followed by ion-pair liquid chromatography-electrospray-mass spectrometry (SPE-IPC-ESI-MS) was used. This work confirmed the little or no effect of primary settlement on total organic carbon (TOC) and monosulfonated compounds removal, whereas the main reduction is obtained at the biological stage. However, the most polar compounds, such as naphthalenedisulfonates (NDS), were not effectively removed using the biological treatment. An aromatic sulfonated compound is suggested to be used as a tracer of the origin of industrial pollutants discharged into STPs. A bioluminescence inhibition test, Microtox assay, allowed toxicity determination of the most relevant aromatic sulfonated compounds detected and toxicity comparison between primary and secondary effluents.     

Distribution and partitioning of phosphorus in solid waste and sediments from drainage canals in the industrial belt of Delhi, India

Phosphorus is an essential and often limiting nutrient in both marine and freshwater ecosystems. However, its oversupply is of great concern in many environments due to its role in eutrophication. The concentration and distribution of sediment bound phosphorus species not only record its input into the environment, but also suggest their possible sources. It is recognized that the features of phosphorus behaviour have not been extensively studied in urban environments. In this study, phosphorus in solid waste and sediments from drainage canals within the industrial belt of Delhi were fractionated into five operationally defined forms, i.e., exchangeable or loosely sorbed phosphorus (Exch-P), Fe-bound phosphorus (Fe-P), authigenic apatite, CaCO3-bound phosphorus and biogenic apatite (Acet-P), detrital apatite (Det-P) and organic-bound phosphorus (Org-P), in order to assess the potential bioavailability status in these systems.     

Long-term increases in surface water dissolved organic carbon: observations, possible causes and environmental impacts

Dissolved organic carbon (DOC) concentrations in 22 UK upland waters have increased by an average of 91% during the last 15 years. Increases have also occurred elsewhere in the UK, northern Europe and North America. A range of potential drivers of these trends are considered, including temperature, rainfall, acid deposition, land-use, nitrogen and CO2 enrichment. From examination of recent environmental changes, spatial patterns in observed trends, and analysis of time series, it is suggested that DOC may be increasing in response to a combination of declining acid deposition and rising temperatures; however it is difficult to isolate mechanisms based on monitoring data alone. Long-term DOC increases may have wide-ranging impacts on freshwater biota, drinking water quality, coastal marine ecosystems and upland carbon balances. Full understanding of the significance of these increases requires further knowledge of the extent of natural long-term variability, and of the natural "reference" state of these systems.     

Temporal variation of trace metal geochemistry in floodplain lake sediment subject to dynamic hydrological conditions

Climate change and land use may significantly influence metal cycling in dynamic river systems. We studied temporal variation of sediment characteristics in a floodplain lake, including concentrations of dissolved organic carbon, acid volatile sulfide and trace metals. The sampling period included a severe winter inundation and a dramatic water level drop during summer. Temporal changes were interpreted using multivariate analysis and chemical equilibrium calculations. Metal concentrations in sediment increased with depth, indicating a gradual improvement of sediment quality. In contrast, dissolved metal concentrations were highest in top layers due to mobilization from oxyhydroxides and precipitation with sulfides in deeper layers. Inundation had a mobilizing effect as it stimulated resuspension and oxygenation of sediment top layers. Water table lowering combined with organic matter decomposition led to immobilization due to sulfide formation. The chemistry of the sediments was consistent with model calculations, especially for macro-elements. The results illustrate the importance of seasonality for metal risk assessment.