Dual-effects of adsorption and photodegradation over titania, silica embedded titania, silica and commercial Degussa P-25 samples were studied for the decolourization of methylene blue in aqueous medium. Silica embedded titania and silica were prepared using inexpensive polymeric version of ethyl silicate as a source of silica. Catalysts were characterized by X-ray diffraction, scanning electron microscopy, UV-Vis spectroscopy and low temperature (77 K) nitrogen adsorption measurements. Among all the catalysts, silica embedded titania has exhibited faster decolourization of methylene blue solution on account of the enhancement of adsorption followed by degradation. An amount of the catalyst and the initial dye concentration of MB solution were found to influence the decolourization activity. Compared to titania catalyst, silica embedded titania and Degussa P-25 have shown the red shift in their UV-Vis spectrum. The experimental data of the reaction fitted well to the pseudo first order kinetic model. In present studies, the adsorption mechanism for the decolourization of MB solution was found to be applicable for an intra particle diffusion model. © 2013 Springer Science+Business Media Dordrecht.

The ubiquitous presence of chlorophenols (CPs) continues to be a cause of concern, owing to their recalcitrant nature. In this context, the present work investigated the degradation of model compounds, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol, by an organic oxidant, methyl ethyl ketone peroxide (MEKP) coupled with ultraviolet irradiation in basic media. Chemical analysis was followed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Despite exhibiting varied patterns of decline, chemical oxygen demand was eventually noted to decrease to the extent of up to 70 %. Simultaneous increase/decrease in the release of chloride ions and decrease in pH indicated that parallel reactions were occurring, which led to the formation of acidic reaction products. First-order dynamics was approximated for all CP congener degradation. The degraded compounds showed absolutely no presence of chlorine atoms, which was a noteworthy feature testifying to the fact that MEKP action was capable of detoxification of CP congeners.

The study of atmospheric concentration levels at a local scale is one of the most important topics in environmental sciences. Multivariate analysis, fuzzy logic, and neural networks have been introduced in forecasting procedures in order to elaborate operational techniques for level characterization of specific atmospheric pollutants at different spatial and temporal scales. Particularly, approaches based on artificial neural networks (ANNs) have been proposed and successfully applied for forecasting concentration levels of PM, NO, SO, CO, and O. The present study explores the development and application of ANN models for forecasting, 24 h ahead, not only the daily concentration levels of PM but also the number of hours exceeding the PM concentration threshold during the day in five different regions within the greater Athens area (GAA). The ANN modeling was based on measurements and estimates of the mean daily PM concentration, the maximum hourly NO concentration, air temperature, relative humidity, wind speed, and the mode daily value of wind direction from five different monitoring stations for the period 2001-2005. The evaluation of the model performance showed the risk of daily PM concentration levels exceeding certain thresholds as well as the duration of the exceedances can be successfully predicted. Despite the limitations of the model, the results indicate that ANNs, when adequately trained, have considerable potential to be used for 1 day ahead PM concentration forecasting and the duration within the GAA.

The subalpine and alpine areas in North-Western Italy and Southern Switzerland (Canton Ticino) receive high deposition of atmospheric pollutants transported from emission sources in the Po Valley. Long-term studies on high-altitude lakes in these areas indicate widespread recovery from acidification, even though most of them are still substantially affected, especially by deposition of nitrogen compounds. We analysed long-term trends of the major chemical compounds in a sample (n = 41) of high-altitude lakes, both at the site and regional levels, with the aim to assess the response of water chemistry to changes in atmospheric deposition and climate. These lakes have been studied since the early 1980s in the context of research programmes on acidification and atmospheric pollution. The significant decrease of sulfate and acidity in atmospheric deposition led to acidification recovery in the majority of the lakes. However, some lakes are still acidic or show a high sensitivity to acidification. This sensitivity is particularly evident at the snowmelt, when alkalinity is still fully depleted in some lakes. At present, nitrate is the dominant acidifying agent in the studied lakes, due to the high input of nitrogen compounds from atmospheric deposition. Our study also demonstrated that climatic factors interact with atmospheric deposition affecting the long-term changes in lake water.

The adsorption mechanism of Ni(II) and Zn(II) onto activated carbon fiber (ACF) cloth and felt plain and oxidized was investigated in this work. The adsorption equilibrium data were obtained in a batch adsorber. The concentration of acidic and basic sites on the ACFS was determined by an acid-base titration method. The experimental adsorption equilibrium data were interpreted with the Redlich-Peterson isotherm, which fitted the data reasonably well. The ACF was oxidized with HNO3 solution and the concentration of acidic sites increased during oxidation, whereas that of the basic sites diminished. The adsorption capacity of the oxidized ACF was higher than that of the plain ACF because the oxidation of ACF formed more acidic sites on the surface where the metal cations can be adsorbed. The adsorption capacity of the plain and oxidized ACFs was linearly dependent upon the concentration of carboxylic sites. The adsorption of Ni(II) and Zn(II) on the ACFs was due to both electrostatic interactions and cation-π interactions. The contribution of ion exchange to the overall adsorption of Zn(II) and Ni(II) on ACFs was less than 3.3 % and can be considered negligible. © 2013 Springer Science+Business Media Dordrecht.

The aim of the present study was to verify if cocaine, at environmental concentrations, influences the endocrine system of the European eel. Silver eels (a stage of the eel life cycle preparing the fish for the oceanic reproductive migration) were exposed to a nominal cocaine concentration of 20 ng/l during 30 days; at the same time, control, carrier, and postexposure recovery groups were made. The effects of cocaine were observed in (1) brain dopamine content, (2) plasma catecholamine levels (dopamine, norepinephrine, and epinephrine), (3) pituitary–adrenal axis activity [plasma adrenocorticotropic hormone (ACTH), corticosterone, cortisol, and aldosterone levels], and (4) pituitary–thyroid axis activity [plasma thyroid-stimulating hormone (TSH), triiodothyronine, and thyroxine levels]. In the treated group, brain dopamine, plasma catecholamines, cortisol, and TSH levels were higher, whereas ACTH, corticosterone, and triiodothyronine levels were lower than controls. In the postexposure recovery group, brain dopamine, plasma dopamine and epinephrine, and thyroxine levels further increased, whereas plasma norepinephrine, cortisol, and corticosterone levels were similar to treated values. Finally, ACTH and TSH were similar, whereas triiodothyronine levels were lower than controls. Aldosterone levels were unaffected by cocaine exposure. The results of the present study show that cocaine, at environmental concentrations, behaves like an endocrine disruptor changing brain dopamine and plasma catecholamine levels and the activity of pituitary–adrenal/thyroid axes. Since the endocrine system plays a key role in the metabolic and reproductive processes of the eel, our results suggest that environmental cocaine could be considered another cause for the decline in the European eel.

Graphene oxide (GO) prepared by modified hummers method was used as adsorbent for removal of heavy metal ions. The oxygenous functional groups on the surface of GO were primarily responsible for the sorption of metal ions. The effects of the parameters of pH value, contact time, Cu(II) concentration, and adsorbent dosage on adsorption were examined. The sorption process conformed to the Freundlich isotherm, and the maximum sorption capacity of 117.5 mg g⁻¹ was observed at an initial pH value of 5.3 after agitating for 150 min. It was also found that Cu-pretreated GO could be desorbed by HCl and the reusability of GO could still maintain above 90 % of its initial capability after ten cycles. The results suggest that GO is an effective adsorbent for copper ions removal in water treatment.

Papaya seed was used as biosorbent for removal of tannery dye (Direct Black 38) from aqueous solution. The papaya seed was characterized, and it posseses macro/mesoporous texture, large pore size, and a surface containing various organic functional groups. The initial dye concentration, contact time, and pH significantly influenced the adsorption capacity. Equilibrium data were analyzed by the Langmuir and Freundlich isotherm models. The equilibrium data were best represented by the Langmuir isotherm, with a high adsorption capacity of 440 mg g⁻¹. Adsorption kinetic data were fitted using the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Boyd models. The adsorption kinetics for the dye onto papaya seed was best described by second-order kinetic equation. The adsorption process mechanism was found to be controlled by both external mass transfer and pore diffusion, but the external diffusion was the dominating process. Papaya seeds showed to be a promising material for adsorption of Direct Black 38 dye from aqueous solution.

The speciation of mercury (Hg) is a major determinant of its methylation rate by sulfate-reducing bacteria (SRB), considered the primary methylators. Under anoxic conditions, sulfur (S) cycling may have a significant influence on Hg complexation and methylation, by influencing both SRB activity and the pool of available reduced S ligands, as the presence of zero-valent sulfur (S(0)) in sulfidic water results in the formation of polysulfides. While SRB frequently coexist with S-oxidizing bacteria in natural environments, the effect that these organisms may have on methylation by SRB is not understood. In this study, we investigate the role of S(0) in methylation by SRB monocultures and cocultures with phototrophic green or purple S-oxidizing bacteria. In the coculture experiments, the presence of S-oxidizers was found to increase Hg methylation rates, apparently by maintaining favorable chemical speciation in the environment. The measured Hg methylation rates were in accord with predictions based on geochemical modeling of speciation. In SRB monoculture experiments conducted in the presence and absence of S(0), the data showed that at limited total Hg, the presence of polysulfides resulted in decreased Hg methylation, presumably by causing a decrease in the most bioavailable Hg–sulfide complexes. These results indicate that models of Hg speciation and methylation in the environment should include a detailed investigation of S redox speciation.

The objectives of this study were to assess susceptibility to acidification and nitrogen (N) saturation caused by atmospheric deposition to northeastern US forests, evaluate the benefits and shortcomings of making critical load assessments using regional data, and assess the relationship between expected risk (exceedance) and forest health. We calculated the critical loads of nutrient N and of sulfur (S) + N using the steady-state mass balance method at >4,000 regional and national vegetation and soil monitoring network plots in the northeastern USA. Regional calculations of critical loads necessitate use of soil maps which provide a range for each soil characteristic resulting in a broad range of critical load of S + N and exceedance values. For the scenario most representative of regional conditions, over 80 % of the critical loads fell into the range of 850–2050 eq ha⁻¹ yr⁻¹; at 45 % of the plots, deposition exceeded the critical load. In contrast, the critical load for nutrient N, 200–300 eq ha⁻¹ yr⁻¹, was lower. Site measurements, especially to estimate soil weathering, would increase the certainty of the critical load. We observed significant negative correlations between critical load exceedance and growth (17 species) and crown density (4 species); we observed significant positive correlations of exceedance with declining vigor (four species), with crown dieback (six species) and crown transparency (seven species). Among the species which demonstrate the most significant detrimental responses to atmospheric deposition are balsam fir, red spruce, quaking aspen, and paper birch. These results indicate that significant detrimental responses to atmospheric deposition are being observed across the northeastern USA.