Zinc removal from synthetic waters using magnetite/graphene oxide composites

The removal of heavy metals from wastewater has become a global challenge, which demands the continuous study of efficient and low-cost treatment alternatives such as adsorption. In this research, the removal of zinc was evaluated using batch adsorption processes with nonconventional materials such as graphene oxide (GO), magnetite (MG), and their composites (GO:MG), formulated with three weight ratios (2:1, 1:1, and 1:2). Graphene was synthesized by the modified Marcano method, using pencil lead graphite as a precursor. MG and the composites were synthesized by chemical coprecipitation of ferrous sulfate and ferric chloride. The materials were characterized by Raman and Fourier transform infrared spectroscopies, scanning electron microscopy, X-ray diffraction, and the Brunauer–Emmett–Teller method to determine the functional groups, microstructural and morphological characteristics, and specific surface area. Batch adsorption tests were carried out to optimize the adsorbent dose and contact time with zinc solutions of 10 ppm. Zinc adsorption reached equilibrium at 2 h, with an optimal dose between 0.25 and 1.0 g/L. The maximum zinc removal efficiencies/adsorption capacities were 98.6%/165.6, 83.4%/47.6, 83.5%/21.9, 72.8%/19.9, and 82.2%/9.25 mg/g using GO, 2GO:1MG, 1GO:1MG, 1GO:2MG, and MG, respectively. Furthermore, the analysis of the isotherm and adsorption kinetics models determined that the adsorption processes using MG and the composites fit the Sips and pseudo-second-order models.     

A fuzzy multi-attribute model for risk evaluation in workplaces

Risk assessment constitutes a critical phase of the safety management process. It basically consists of evaluating the risks involved in the execution of working activities, so as to provide the managers with information suitable to address intervention measures. The most important activity in risk assessment is the risk evaluation task but, despite its importance, national and international regulations have never formalized a standard methodology for addressing it, leaving companies complete freedom to adopt the approach they consider appropriate. As a consequence, companies generally settle on the use of simple methodologies which frequently are not able to emphasize all the main aspects affecting risk in the workplace and to produce a precise ranking of hazardous activities. In this paper, a new methodology for risk evaluation is then proposed with the aim to overcome limitations of the classical approaches. In particular, new factors are introduced to take into account effects of human behavior and environment on risk level, other than the classical injury magnitude and occurrence probability of an accident. The proposed methodology also integrates an estimative approach based on the fuzzy logic theory, which permits more coherence in the evaluation process, producing a very suitable final rank of hazardous activities. Finally, an actual case study is reported to show the capabilities of the new risk evaluation model.     

Monitoring water quality in reservoirs for human supply through multi-biomarker evaluation in tropical fish

Paraíba do Sul River is located at a very densely inhabited region of Brazil crossing the three most industrialized states of the country (S?o Paulo, Minas Gerais and Rio de Janeiro states). As a result, industrial and farming residues as well as urban sewage are frequently disposed without appropriate treatment. The current study aimed at investigating the water quality in three reservoirs along the Paraíba do Sul River (Ilha dos Pombos, Santa Cecília and Santa Branca), through physiological, morphological, biochemical, and genetic biomarkers. The bioindicator chosen was the catfish Pimelodus maculatus, sampled during the dry (June 2008) and rainy (February 2009) seasons. Also, some water physicochemical parameters were analyzed from the sampling sites, but displayed no alterations according to the Brazilian Agency for Water Quality Legislation. Branchial carbonic anhydrase activity was inhibited in the dry season, while renal carbonic anhydrase activity was inhibited in the rainy season in the Santa Branca reservoir, indicating disturbance of osmoregulatory and acid-base regulation processes. Histopathological alterations were observed in the gills (neoplasic and tissue hyperplasia processes) and liver (necrosis), indicating serious damage to the functional integrity of these organs. A high incidence of melanomacrophage centers was observed in the liver, suggesting an intense immune response in all reservoirs. Acetylcholinesterase and catalase activity showed also differences corroborating some morphological results. Likewise, the induction of the micronucleus and DNA damage indicate genotoxicity, but mainly in the Santa Branca reservoir. Thus, the health status of P. maculatus warrants caution in the use of the water from the 3 reservoirs for direct human consumption, particularly after the accidental spill of endosulfan in November 2008, three months before the rainy season sampling.     

Spectral trend of vegetation with rainfall in events of El Niño-Southern Oscillation for Atlantic Forest biome,Brazil

This study aimed to analyze the spectral trend of vegetation with rainfall in El Niño-Southern Oscillation events (ENSO) in the Atlantic Forest, Brazil. Monthly rainfall data were collected from 85 conventional meteorological stations (EMC), data from the Enhanced Vegetation Index 2 (EVI2) and ENSO events (El Niño, La Niña, and Neutral) in the period from 2001 to 2013. Afterwards, state cluster analysis was performed using the results of non-parametric tests. The Mann-Kendall (MK) non-parametric test did not identify a trend pattern in rainfall distribution in the Atlantic Forest. The results for EVI2 by state and region showed that the trend is decreasing in the Northeast Region, except for the states of Alagoas and Pernambuco. Southeast region showed an increasing trend of EVI2 (except for Rio de Janeiro and São Paulo), while the South region showed a decreasing trend. In the Midwest, the trend was significantly decreasing. In the prognosis elaborated for the future, the regions with significant declines of the vegetation were the Northeast and Midwest. This study shows that the Atlantic Forest in some regions of Brazil has been suffering from the growing urbanization process and there is a trend of soil degradation.     

The impact of global change on economic values of water for Public Irrigation Schemes at the São Francisco River Basin in Brazil

Economic values of water for the main Public Irrigation Schemes in the sub-middle region of the São Francisco River Basin, in northeastern Brazil, are determined in this study using an integration of a global agro-economic land and water use (MAgPIE) with a local economic model (Positive Mathematical Programming). As in the latter, the water values depend on the crops grown, and as Brazilian agriculture is strongly influenced by the global market, we used a regionalized version of the global model adapted to the region in order to simulate the crop land use, which is in turn determined by changes in global demand, trade barriers, and climate. The allocation of sugarcane and fruit crops projected with climate change by the global model, showed an impact on the average yields and on the water costs in the main schemes resulting in changes in the water values locally. The economic values for all schemes in the baseline year were higher than the water prices established for agricultural use in the basin. In the future, these water values will be higher in all the schemes. The highest water values currently and in the future were identified in municipalities with a significant proportion of area growing irrigated sugarcane. Being aware of current water values of each user in a baseline year and in a projected future under global climate and socioeconomic changes, decision makers should improve water allocation policies at local scale, in order to avoid conflicts and unsustainable development in the future.     

Dynamics of leaf litter and soil respiration in a complex multistrata agroforestry system,Pernambuco, Brazil

High litter inputs in agroforestry systems contribute to soil microbial activity, soil fertility and productivity. Considering that the cycling of organic matter is essential to the maintenance of physical–chemical and microbiological properties of the soil, the aims of this work were to estimate the production, accumulation and decomposition of litter, and assess soil microbial respiration in a complex multistrata agroforestry system located in the north-east of Brazil. This agroforestry system has three strata formed by forest and fruit trees and species of multiple uses. During 3 years (2011–2013), leaf litter was sampled monthly to account for litterfall and quarterly to account for litter accumulation. The rates of litter decomposition were estimated using the ratio produced-to-accumulated litter, and the correlation between litter fall and rainfall was calculated. Precipitation data were provided by the water and climate agency of Pernambuco (APAC). Soil samples (0–15 cm) were also taken quarterly, simultaneously with the litter accumulation samples, and soil microbial respiration was assessed using the capture, by a KOH solution, of the evolved CO₂. The annual production of leaf litter was stable in the 3 years of study in this agroforestry system, and the monthly input of litter to the soil was influenced by rainfall, being higher in the dry seasons. The accumulated litter on the ground was constant, as was microbial activity (respiration) through time. The estimated litter decomposition rates were 1.49 (first year), 1.33 (second year) and 1.42 (third year), being considered rapid rates of decomposition. This guarantees (to the farmer) that this system is capable of maintaining soil fertility and eliminates the need for chemical fertilizers.     

Forensic Evaluation of Metals (Cr,Cu, Pb,Zn), Isotopes (δ13C and δ15N), and C:N Ratios in Freshwater Sediment

A forensic approach was used to evaluate sediments from Portão Stream, including analysis of metals, carbon (C) and nitrogen (N) stable isotopes, and C:N ratios. Samples collected at various points located along the stream were tested in order to investigate a possible illegal leachate input. The studied stream is heavily impacted by sewage and industrial discharges from two cities along its course. Among the metals analyzed, chromium (Cr) was noticeably the main pollutant, showing the highest levels, above regulatory limits, downstream from some potential sources of effluents enriched with this metal. Isotope analyses revealed a general trend of depletion in the heavier isotope along the stream for C and N. The exception was one point near a hazardous waste landfill, where relatively more enriched δ¹³C and δ¹⁵N values were found. The isotope and metal analysis results indicated that this site was affected by a particular source, demonstrating the combination of these parameters could be used for the discrimination of sources in a heavily polluted stream. Nevertheless, further investigations are necessary to provide a comprehensive evaluation of the biogeochemical processes involved in the incorporation of leachate in sediments to use this analysis as evidence for the illegal leachate discharge.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

The role of place identity and place attachment in breaking environmental protection laws

Place identity and place attachment have been related to several environmental variables such as appropriation, residential satisfaction, physical care taken of the neighbourhood, restorativeness, environmental attitudes and, especially, pro-environmental behaviour. However, the role of place identity and place attachment has not been analyzed in relation to anti-ecological behaviours such as transgressions of environmental protection laws. The aim of this study is to analyze the relationship of place identity, place attachment and environmental attitudes to the personal and social norms that explain the likelihood of illegal behaviours against the environment. The sample was composed of men and women, aged from 19 to 70 years, who were resident in rural, urban or tourist areas of a territory under high environmental protection. The strongest predictor of environmental transgression is personal norms, whereas place identity and place attachment have no direct relation with future transgression or personal norms. Place identity influences environmental attitudes and social norms, which are both antecedents of personal norms. The results led us to reconsider the efficacy of interventions aimed at encouraging compliance with environmental laws by only emphasizing individuals' bonds with the environment, and the need to extend the study of the role of personal and social norms in environmental protection.