Competitive sorption of cis-DCE and TCE in silica gel as a model porous mineral solid

The competitive sorption of 1,2-cis-dichloroethene (cis-DCE) and trichloroethene (TCE) was investigated by means of column experiments using a model porous mineral solid represented by silica gel. The experimental isotherms were obtained by employing a chromatographic method. The competitive sorption isotherms were modelled with the extended Freundlich and extended Langmuir isotherms, using the parameters from single-solute experiments. The breakthrough curves were modelled with the advection-dispersion transport equation coupled with the lumped pore diffusion model. The best results were obtained when the extended Freundlich isotherm was employed. The competitive sorption was revealed with the presence of an overshoot in the breakthrough curve of cis-DCE and a decrease in the degree of sorption of cis-DCE (20%) and TCE (12%). A linear dependency of the overshoot with an increase in the concentration of cis-DCE at a fixed concentration of TCE was observed, between 16% and 20%, and at least at concentrations <6 mg L(-1) in the liquid phase. The displaced molecules of cis-DCE by TCE were accumulated through the column causing its overshoot; thus short columns may hinder its observation. Thermodynamic analysis shows an exothermic adsorption process of -34 to -41 kJ mol(-1), which is enhanced by sorption in micropores. The Gibbs free energy is positive for cis-DCE in the multi-component case, due to its displacement by TCE.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Influence of different abiotic and biotic factors on the metalaxyl and carbofuran dissipation

Metalaxyl and carbofuran dissipation was studied in response to different factors (soil bacterial communities, light irradiation, presence of an inorganic culture medium and presence of soil) and combinations of these factors in short-term experiments (48 h). The soil microbial communities have no effect on metalaxyl or carbofuran dissipation in the time scale employed. Light irradiation and soil promote metalaxyl and carbofuran dissipation by photodegradation and adsorption, respectively. However, photodegradation has a stronger effect on metalaxyl and carbofuran dissipation than the adsorption of the pesticides in the soil. The addition of the culture medium have no direct effect on pesticide dissipation, degradation by microbial communities or adsorption but its presence greatly increased photodegradation.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10^?4 s^?1; 1 × 10^?4 s^?1; and 2 × 10^?5 s^?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10^{? 3} h^{? 1} to 7.0 × 10^{? 3} h^{? 1}. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Comparison of batch, stirred flow chamber, and column experiments to study adsorption, desorption and transport of carbofuran within two acidic soils

Different methods (batch, column and stirred flow chamber experiments) used for adsorption and desorption of carbofuran studies were compared. All tested methods showed that the carbofuran adsorption was higher in the soil with the higher organic matter content, whereas the opposite behaviour was observed for the percentage of carbofuran desorbed. However, different methods have revealed some discrepancies in carbofuran adsorption/desorption kinetics. Although batch method showed interesting data on equilibrium experiments, such as a low heterogeneity for the carbofuran adsorption sites independent of soil organic matter content, it had some disadvantages for carbofuran adsorption/desorption kinetic studies. The disadvantages were related with the excessive limitations of this method on kinetics, i.e., no difference could be detected between different soils. However, with column and stirred flow chamber methods the carbofuran adsorption/desorption kinetics of different soils could be compared. Moreover, the absolute values of carbofuran adsorption/desorption and its rate were higher in the stirred flow chamber than in the batch and column experiments. Using stirred flow chamber experiments the carbofuran desorption was significantly faster than its adsorption, whereas carbofuran using column experiments they were similar. These discrepancies should be considered when the results obtained only with one method is discussed.     

Solar photocatalytic treatment of landfill leachate using a solid mineral by-product as a catalyst

The treatment of municipal solid waste landfill leachate in a pilot plant made up of solar compound parabolic collectors, using a solid industrial titanium by-product (WTiO₂) containing TiO₂ and Fe(III) as a photocatalyst, was investigated. In the study evidence was found showing that the degradation performed with WTiO₂ was mainly due to the Fe provided by this by-product, instead of TiO₂. However, although TiO₂ had very little effect by itself, a synergistic effect was observed between Fe and TiO₂. The application of WTiO₂, which produced coupled photo-Fenton and heterogeneous catalysis reactions, achieved a surprisingly high depuration level (86% of COD removal), higher than that reached by photo-Fenton using commercial FeSO₄ (43%) in the same conditions. After the oxidation process the biodegradability and toxicity of the landfill leachate were studied. The results showed that the leachate biodegradability was substantially increased, at least in the first stages of the process, and again that WTiO₂ was more efficient than FeSO₄ in terms of increasing biodegradability.     

Management of invasive populations of the freshwater crayfish <Emphasis Type="Italic">Procambarus clarkii</Emphasis> (Decapoda,Cambaridae): test of a population-control method and proposal of a standard monitoring approach

Invasive species are one of the main threats to biodiversity. When an alien species is introduced into a new environment, fast identification and definition of management strategies may avoid or minimize impacts. When an invasive species is already established, the most adopted approaches are population control and monitoring. In order to perform such strategies, assessment of characteristics of the invasive population is imperative. This study tested a new method of population size estimation and monitoring in an invasive population of crayfish Procambarus clarkii in a conservation area in the Atlantic Rain Forest (Southeastern Brazil). The population dynamics was studied for 1 year to examine the efficacy of the selected method and to evaluate if the population is stable. Later, the effect of periodical removal of animals on the population size was tested. The method of population estimation used in this study proved to be very effective. We recommend using it to monitor invasive populations of P. clarkii. The population size varied discretely over the year with variable but low growth rate, indicating that the population is already established which introduce a notable threat to native species. The continuous removal of specimens proved to be inefficient since the growth rate was higher after the removal. One intensive removal event might be more effective than a continuous moderate removal as the one applied in this study.     

Spanish agriculture from 1900 to 2008: a long-term perspective on agroecosystem energy from an agroecological approach

Regional Environmental Change - According to the agroecological approach, energy analyses applied to agriculture should provide information about the structure and functions of the agroecosystem;...     

Butyltin compounds and their relation with organic matter in marine sediments from San Vicente Bay—Chile

Tributyltin and its degradation products, mono-and dibutyltin have been determined in sediments collected in some representative sites in San Vicente Bay, Chile. The organic matter contents of sediments and water collected simultaneously from the same sampling sites were also determined. High levels of total organic carbon were found in sediments, especially in those from the northern part of the bay (1.80-8.87%). Good correlations were found between total organic carbon and the oxidizable and refractory carbon fractions. Among the butyltin species determined, TBT presented the highest levels, ranging from 14 to 1,560 ng Sn g(-1) dry weight. Concentration ratios of TBT to DBT ranged between 1.33 and 3.10, showing a high degree of contamination in sediments of this Chilean bay. All data obtained were analysed by the chemometric method of principal components analysis. A strong correlation was found between TBT and DBT concentrations in sediments, the different organic matter contents in sediments and water. In marine organisms only TBT was detected, containing the filterer organism Semele solida higher level than Perumytilus purpuratus and Pyura chilensis (220, 150 and 120 ng Sn g(-1) dry weight, respectively). For the alga Rodoficea iridae the TBT concentration was 60 ng Sn g(-1) dw. Comparatively, these values are higher than those reported for the same kind of marine organisms worldwide. The different samples from San Vicente Bay were found to be contaminated by TBT. This contamination can be attributed to the different anthropogenic activities taking place in the bay.