Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

Effect of gaseous chlorine dioxide on indoor microbial contaminants

Traditional and modern techniques for bioaerosol enumeration were used to evaluate the relative efficiency of gaseous chlorine dioxide (ClO2) in reducing the indoor microbial contamination under field and laboratory conditions. The field study was performed in a highly microbially contaminated house, which had had an undetected roof leak for an extended period of time and exhibited large areas of visible microbial growth. Air concentrations of culturable fungi and bacteria, total fungi determined by microscopic count and polymerase chain reaction (PCR) assays, endotoxin, and (1 --> 3)-beta-D-glucan were determined before and after the house was tented and treated with ClO2. The laboratory study was designed to evaluate the efficiency of ClO2 treatment against known concentrations of spores of Aspergillus versicolor and Stachybotrys chartarum on filter paper (surrogate for surface treatment). These species are commonly found in damp indoor environments and were detected in the field study. Upon analysis of the environmental data from the treated house, it was found that the culturable bacteria and fungi as well as total count of fungi (as determined by microscopic count and PCR) were decreased at least 85% after the ClO2 application. However, microscopic analyses of tape samples collected from surfaces after treatment showed that the fungal structures were still present on surfaces. There was no statistically significant change in airborne endotoxin and (1 --> 3)-beta-D-glucan concentration in the field study. The laboratory study supported these results and showed a nonsignificant increase in the concentration of (1 --> 3)-beta-D-glucan after ClO2 treatment.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Use of electrochemical technology to increase the quality of the effluents of bio-oxidation processes. A case studied

In this work, it has been studied the use of conductive-diamond electrochemical oxidation (CDEO) as a refining technology to assure the quality of the effluents of door manufacturing processes (DMP). To do this, the raw effluents of these factories have been treated by a combination of physicochemical, biological and CDEO treatments. CDEO was found to be a feasible alternative to the refinement of a wooden DMP waste. It can successfully decrease the organic load of the effluents of the biological oxidation with low energy requirements. In addition, in case of incidents in the biological process, CDEO can treat successfully the effluents of the coagulation process. The effluents of the biological treatment have also been treated by CDEO in order to check the possible use of electrochemical technology to increase the biodegradability of the effluents and their possible recycle to the biological treatment. Unfortunately, electrochemical technology was found to be not adequate to increase the biodegradability of the effluents of a biological treatment. The hard oxidation conditions generated during CDEO do not lead to the accumulation of intermediates but to the almost direct formation of carbon dioxide. Lowering the current density or changing the electrodes can not enhance the biodegradability of the effluents of an electrochemical cell.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

Nonlinear regression adjustments of multiple continuous monitoring methods produce effective characterization of short-term fine particulate matter

This study comprehensively characterizes hourly fine particulate matter (PM(2.5)) concentrations measured via a tapered element oscillating microbalance (TEOM), beta-gauge, and nephelometer from four different monitoring sites in U.S. Environment Protection Agency (EPA) Region 5 (in U.S. states Illinois, Michigan, and Wisconsin) and compares them to the Federal Reference Method (FRM). Hourly characterization uses time series and autocorrelation. Hourly data are compared with FRM by averaging across 24-hr sampling periods and modeling against respective daily FRM concentrations. Modeling uses traditional two-variable linear least-squares regression as well as innovative nonlinear regression involving additional meteorological variables such as temperature and humidity. The TEOM shows a relationship with season and temperature, linear correlation as low as 0.7924 and nonlinear model correlation as high as 0.9370 when modeled with temperature. The beta-gauge shows no relationship with season or meteorological variables. It exhibits a linear correlation as low as 0.8505 with the FRM and a nonlinear model correlation as high as 0.9339 when modeled with humidity. The nephelometer shows no relationship with season or temperature but a strong relationship with humidity is observed. A linear correlation as low as 0.3050 and a nonlinear model correlation as high as 0.9508 is observed when modeled with humidity. Nonlinear models have higher correlation than linear models applied to the same dataset. This correlation difference is not always substantial, which may introduce a tradeoff between simplicity of model and degree of statistical association. This project shows that continuous monitor technology produces valid PM(2.5) characterization, with at least partial accounting for variations in concentration from gravimetric reference monitors once appropriate nonlinear adjustments are applied. Although only one regression technically meets new EPA National Ambient Air Quality Standards (NAAQS) Federal Equivalent Method (FEM) correlation coefficient criteria, several others are extremely close, showing optimistic potential for use of this nonlinear adjustment model in garnering EPA NAAQS FEM approval for continuous PM(2.5) sampling methods.     

Functionally relevant microorganisms to enhanced biological phosphorus removal performance at full-scale wastewater treatment plants in the United States

The abundance and relevance ofAccumulibacter phosphatis (presumed to be polyphosphate-accumulating organisms [PAOs]), Competibacter phosphatis (presumed to be glycogen-accumulating organisms [GAOs]), and tetrad-forming organisms (TFOs) to phosphorus removal performance at six full-scale enhanced biological phosphorus removal (EBPR) wastewater treatment plants were investigated. Coexistence of various levels of candidate PAOs and GAOs were found at these facilities. Accumulibacter were found to be 5 to 20% of the total bacterial population, and Competibacter were 0 to 20% of the total bacteria population. The TFO abundance varied from nondetectable to dominant. Anaerobic phosphorus (P) release to acetate uptake ratios (P(rel)/HAc(up)) obtained from bench tests were correlated positively with the abundance ratio of Accumulibacter/(Competibacter +TFOs) and negatively with the abundance of (Competibacter +TFOs) for all plants except one, suggesting the relevance of these candidate organisms to EBPR processes. However, effluent phosphorus concentration, amount of phosphorus removed, and process stability in an EBPR system were not directly related to high PAO abundance or mutually exclusive with a high GAO fraction. The plant that had the lowest average effluent phosphorus and highest stability rating had the lowest P(rel)/HAc(up) and the most TFOs. Evaluation of full-scale EBPR performance data indicated that low effluent phosphorus concentration and high process stability are positively correlated with the influent readily biodegradable chemical oxygen demand-to-phosphorus ratio. A system-level carbon-distribution-based conceptual model is proposed for capturing the dynamic competition between PAOs and GAOs and their effect on an EBPR process, and the results from this study seem to support the model hypothesis.     

The lanthanum precipitation method. Part 1: a new method for technetium(IV) speciation in humic rich natural groundwater

A new and quick method for direct speciation of Tc(IV) in humic rich solutions, based on the induced aggregation of humic substances in the presence of the trivalent cation La(3+), is presented. This method (the "La-precipitation method") allows flocculating all the humic substances and also the Tc(IV) associated with humic substances. The method is tested on solutions containing Tc(IV) and Gorleben humic substances. The influence of different parameters (humic substance concentration, Tc concentration, reaction time and pH) is investigated on the observed free Tc(IV) concentration after precipitation of all humic substances. None of these parameters had a (significant) influence on the observed Tc(IV) concentration in solution after addition of La(3+) to Tc(IV)-HS containing solutions. It is therefore proposed that the method can be used to separate the Tc(IV) bound to humic substances from the free inorganic Tc species in solution.