Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake. Copyright © Taylor & Francis Group, LLC.

Radial basis function networks with quantized parameters

A RBFN implemented with quantized parameters is proposed and the relative or limited approximation property is presented. Simulation results for sinusoidal function approximation with various quantization levels are shown. The results indicate that the network presents good approximation capability even with severe quantization. The parameter quantization decreases the memory size and circuit complexity required to store the network parameters leading to compact mixed-signal circuits proper for low-power applications. ©2008 IEEE.

The role of coarse intermetallics in the localized corrosion behaviour of AA 2024-T3 in low concentrated chloride media

Aluminium alloy (AA) 2024-T3 is an important engineering material due to its widespread use in the aerospace industry. However, it is very prone to localized corrosion attack in chloride containing media, which has been mainly associated to the presence of coarse intermetallics (IMs). In this work the corrosion behaviour of aluminium alloy 2024-T3 in low concentrated chloride media was investigated using microscopy and electrochemical methods. SEM observations have shown that intermetallics with the same nominal composition present heterogeneous reaction rates, and that both types of coarse IMs normally found in the AA 2024-T3 microstructure corrode. Moreover, EDS analyses have shown important compositional changes in the corroded IMs, evidencing the selective corrosion of their more active constituents and the onset of an intense oxygen peak, irrespective to the IM nature. TEM/EDS observations on non-corroded samples have evidenced the heterogeneous composition within the IMs. On the other hand, the results of the electrochemical investigations, in accordance with the SEM/EDS observations, have evidenced that IMs corrosion dominates the electrochemical response of the alloy during the first hours of immersion in the test electrolyte. © 2009 by NACE International.

The effect of chloride ions and A. ferrooxidans on the oxidative dissolution of the chalcopyrite evaluated by electrochemical noise analysis (ENA)

It is believed that the dissolution of chalcopyrite (CuFeS2) in acid medium can be accelerated by the addition of Cl- ions, which modify the electrochemical reactions in the leaching system. Electrochemical noise analysis (ENA) was utilized to evaluate the effect of the Cl- ions and Acidithiobacillus ferrooxidans on the oxidative dissolution of a CPE-chalcopyrite (carbon paste electrode modified with chalcopyrite) in acid medium. The emphasis was on the analysis of the admittance plots (Ac) calculated by ENA. In general, a stable passive behavior was observed, mainly during the initial stages of CPE-chalcopyrite immersion, characterized by a low passive current and a low dispersion of the Ac plots, mainly after bacteria addition. This can be explained by the adhesion of bacterial cells on the CPE-chalcopyrite surface acting as a physical barrier. The greater dispersions in the Ac plots occurred immediately after the Cl- ions addition, in the absence of bacteria characterizing an active-state. In the presence of bacteria the addition of Clions only produced some effect after some time due to the barrier effect caused by bacteria adhesion. © (2009) Trans Tech Publications.

Crescimento de mudas de Schizolobium amazonicum (Huber ex Ducke) em substrato fertilizado com nitrogênio, fósforo e potássio

The nutritional management of seedlings in the nursery is one of the most important practices that influence seedling quality. The aim of this work was to evaluate the effect of nitrogen, phosphorus and potassium on the development of Schizolobium amazonicum seedlings grown in 250 cm containers with a commercial substrate in the North of Mato Grosso State, Brazil. The experimental design was completely randomized design with five treatments and five replications, each replication being represented by 24 seedlings. The treatments were: control (only commercial substrate); nitrogen fertilization (150 g m-3 N using ammonium sulfate + 1.0 kg of ammonium sulfate dissolved in 100 L of water and applied in coverage); phosphorus fertilization (300 g P2O 5 m-3 using simple superphosphate); potassium fertilization (100 g m-3 K2O using potassium chloride + 0.3 kg of potassium chloride dissolved in 100 L of water and applied in coverage) and; complete (a mixture of the three nutrients, 150, 300 and 100 g m-3 N, P2O5 and K2O, respectively + 1.0 kg of ammonium sulfate + 0.3 kg of potassium chloride). The commercial substrate was composted milled pine bark plus vermiculite. Evaluations of the seedlings were performed at 90 days after sowing. The complete treatment (NPK) gave the highest values for biometric and best plant indices, which express the quality. When analyzing nutrients in isolation; potassium had the lowest effect. Based on these results it can be recommended to fertilize Schizolobium amazonicum seedlings in nurseries with 150, 300 and 100 g m-3 of N, P2O5 and K2O, respectively, plus 1.0 kg of sulfate ammonium and 0.3 kg of potassium chloride applied in coverage.

Formation of silver chloride nanocrystals as a corrosion product of silver in H2SO4 solution

The purpose of this study is to characterize the corrosion product on the surface of silver, employing H2SO4 (0.5M) as electrolyte. The electrochemical parameters, Ecor, Icor, V cor and Rp were obtained after analyzing the potentiodynamic polarization curve in which two peaks were observed. The smallest (passive region) is attributed to the Cl- traces from the reference electrode, with micro-cracks. The second peak (in the transpassivation region) corresponds to the polarization curve of silver in H2SO 4 without contaminants. SEM images and EDS analysis reveal images of a surface layer on silver, consisting of structures containing sulfur, oxygen, silver and chloride, as the corrosion product. On this layer silver sulfate crystals were observed, which occurs during the formation of silver chloride nanocrystals with different morphologies, when chloride ions were added to the electrolyte medium. ©The Electrochemical Society.

Thermo-gravimetric analysis (TGA) after different exposures of high density polyethylene (HDPE) and poly vinyl chloride (PVC) geomembranes

This paper presents the results of thermogravimetric analysis (TGA) tests in PVC (1.0; 2.0 mm) and HDPE (0.8; 2.5 mm) geomembranes exposed to weathering and leachate after 30 months. The aim of this paper is the comparison of fresh and exposed samples to assess the degradation process concerning the total loss of mass of geomembranes. The exposure was conducted in accordance with the recommendations of ASTM standards. The TGA tests were carried out according to ASTM D6370 and E2105. Results show, for instance, that for PVC geomembrane the largest reductions of plasticizers occurred for samples exposed to weathering. The loss of plasticizers after the exposure contributed to the decrease of deformation and consequent increase in stiffness. TGA tests shows to be a valuable tool to control the quality of the materials. © 2012 ejge.

Voltammetric determination of ethyl acetate in ethanol fuel using a Fe 3+/Nafion®-coated glassy carbon electrode

A voltammetric method for the determination of ethyl acetate in ethanol fuel using a Fe3+/Nafion®-coated glassy carbon electrode (GCE) is proposed. The ethyl acetate present in the ethanol fuel was previously converted to acetohydroxamic acid via pretreatment with hydroxylamine chloride. The acetohydroxamic acid promptly reacted with the iron (III) present in the film, producing iron (III) acetohydroxamate, which presents a well-defined voltammetric peak current at -0.02 V. Optimization of the voltammetric parameters for the cyclic, linear sweep, square wave, and differential pulse modalities was carried out for this chemically-modified electrode. Square wave voltammetry afforded the best response for acetohydroxamic acid detection. The analytical curve for this species was linear from 9 to 100 μmol L 1 according to the following equation: ip (μA) = 0.27 + 2.55Cacetohydroxamic acid (μmol L 1), with linear correlation coefficient equal to 0.993. The technique presented limit of detection equal to 5.3 μmol L 1 and quantification limit of 17.6 μmol L 1. The proposed method was compared to the official method of ethyl acetate analysis (Gas Chromatography), and a satisfactory correlation was found between these techniques. © 2012 Elsevier Ltd. All rights reserved.

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI-MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (1H-13C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple-Bond Correlation (HMBC), 1H-15N HMBC, 1H- 1H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p-Cl and p-Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p-NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.

Design of biogas pipeline - Energy and sanitation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of Na-chloride on the bioleaching of a chalcopyrite concentrate in shake flasks and stirred tank bioreactors

Oxidative dissolution of chalcopyrite at ambient temperatures is generally slow and subject to passivation, posing a major challenge for developing bioleaching applications for this recalcitrant mineral. Chloride is known to enhance the chemical leaching of chalcopyrite, but much of this effect has been demonstrated at elevated temperatures. This study was undertaken to test whether 100-200 mM Na-chloride enhances the chemical and bacterial leaching of chalcopyrite in shake flasks and stirred tank bioreactor conditions at mesophilic temperatures. Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and abiotic controls were employed for the leaching experiments. Addition of Na-chloride to the bioleaching suspension inhibited the formation of secondary phases from chalcopyrite and decreased the Fe(III) precipitation. Neither elemental S nor secondary Cu-sulfides were detected in solid residues by X-ray diffraction. Chalcopyrite leaching was enhanced when the solution contained bacteria, ferrous iron and Na-chloride under low redox potential (< 450 mV) conditions. Scanning electron micrographs and energy-dispersive analysis of X-rays revealed the presence of precipitates that were identified as brushite and jarosites in solid residues. Minor amounts of gypsum may also have been present. Electrochemical analysis of solid residues was in concurrence of the differential effects between chemical controls, chloride ions, and bacteria. Electrochemical impedance spectroscopy was used to characterize interfacial changes on chalcopyrite surface caused by different bioleaching conditions. In abiotic controls, the impedance signal stabilized after 28 days, indicating the lack of changes on mineral surface thereafter, but with more resistive behavior than chalcopyrite itself. For bioleached samples, the signal suggested some capacitive response with time owing to the formation of less conductive precipitates. At Bode-phase angle plots (middle frequency), a new time constant was observed that was associated with the formation of jarosite, possibly also with minor amount or elemental S, although this intermediate could not be verified by XRD. Real impedance vs. frequency plots indicated that the bioleaching continued to modify the chalcopyrite/solution interface even after 42 days. © 2013 The Authors.

Evaluation of the chemical interaction between carbon nanotubes functionalized with TGDDM tetrafunctional resin and hardener DDS

In this work, the chemical interaction between carbon nanotubes (MWCNT) functionalized with acyl chloride (SOCl2) and polymer chain tetrafuncional N,N,N′,N′-tetraglycidyl-4,4′- diaminodiphenylmethane (TGDDM) and hardener 4,4′diaminodiphenyl sulfone (DDS) has been monitored by Fourier transform infrared spectroscopy (FTIR) with a attenuated total reflectance (ATR) coupled. MWCNT were obtained from the pyrolysis of a mixture of camphor and ferrocene into a oven. The functionalization process was done by oxidative treatment in order to incorporate carboxylic group over the walls of MWCNT, before to be used SOCl2. The functionalized carbon nanotubes were evaluated by X-ray photoelectron spectroscopy (XPS), Raman and transmission electron microscopy (TEM). Nanostructured composites were processed by using epoxy resin with MWCNT in varying percentages. In this work it was observed that different percentages of functionalized nanotubes modify the interaction between the composite matrix and curing agent, where can be observed that in specimens with content less than 1 wt% MWCNT the chemical bond occurs preferentially from the opening of the SO double bond of the hardener and when is used MWCNT content higher than 1 wt% there is little chemical interaction with the SO bond of the hardener and most MWCNT binds to amine. © 2013 Elsevier Ltd.

Anthropogenic impacts on mineral weathering: A statistical perspective

Correspondence Analysis was adopted as tool for investigating the statistical structure of hydrochemical and weathering datasets of groundwater samples, with the main purpose of identifying impacts on mineral weathering caused by anthropogenic activities, namely fertilizing of farmlands. The hydrochemical dataset comprised measured concentrations of major inorganic compounds dissolved in groundwater, namely bicarbonate, silica (usually by-products of chemical weathering), chloride, sulphate and nitrate (typically atmospheric plus anthropogenic inputs). The weathering dataset consisted of calculated mass transfers of minerals being dissolved in loess sediments of a region located in SW Hungary (Szigetvár area), namely Na-plagioclase, calcite and dolomite, and of pollution-related concentrations of sodium, magnesium and calcium. A first run of Correspondence Analysis described groundwater composition in the study area as a system of triple influence, where spots of domestic effluents-dominated chemistries are surrounded by areas with agriculture-dominated chemistries, both imprinted over large regions of weathering dominated chemistries. A second run revealed that nitrification of N-fertilizers is promoting mineral weathering by the nitric acid reaction (anthropogenic pathway), in concurrence with the retreating of weathering by carbonic acid (natural pathway). It also indicated that dolomite and calcite are being players in a dedolomitization process driven by dissolution of gypsum fertilizers and nitrification of N-fertilizers. © 2013 Elsevier Ltd.

Flexible magnetic membranes based on bacterial cellulose and its evaluation as electromagnetic interference shielding material

Flexible magnetic membranes with high proportion of magnetite were successfully prepared by previous impregnation of the never dried bacterial cellulose pellicles with ferric chloride followed by reduction with sodium bisulfite and alkaline treatment for magnetite precipitation. Membranes were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating magnetometer, field emission scanning electron microscopy (FEG-SEM) and impedance spectroscopy. Microwave properties of these membranes were investigated in the X-band (8.2 to 12.4 GHz). FEG-SEM micrographs show an effective coverage of the BC nanofibers by Fe 3O4 nanoparticles. Membranes with up to 75% in weight of particles have been prepared after 60 min of reaction. Magnetite nanoparticles in the form of aggregates well adhered to the BC fibers were observed by SEM. The average crystal sizes of the magnetic particles were in the range of 10 ± 1 to 13 ± 1 nm (estimated by XRD). The magnetic particles in the BC pellicles presented superparamagnetic behavior with a saturation magnetization in the range of 60 emu g- 1 and coercive force around 15 Oe. These magnetic pellicles also displayed high electrical permittivity and a potential application as microwave absorber materials. © 2013 Elsevier B.V.