Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Study of the degradation of dyes by MnP of Phanerochaete chrysosporium produced in a fixed-bed bioreactor

The production of ligninolytic enzymes by the fungus Phanerochaete chrysosporium in a fixed-bed tubular bioreactor, filled with cubes of nylon sponge, operating in semi-solid-state conditions, was studied. Maximum individual manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of 1293 and 225 U/l were detected.The in vitro decolourisation of two structurally different dyes (Poly R-478, crystal violet) by the extracellular liquid obtained in the above-mentioned bioreactor was monitored in order to determine its degrading capability. The concentration of some compounds (sodium malonate, manganese sulphate) from the reaction mixture was optimised in order to maximise the decolourisation levels. A percentage of Poly R-478 decolourisation of 24% after 15 min of dye incubation was achieved.On the other hand, a methodology for a long treatment of these dyes based on the continuous addition of MnP enzyme and H(2)O(2) was developed. Moreover, this enzymatic treatment was compared with a photochemical decolourisation process. The former allowed to maintain the degradation rate almost constant for a long time, resulting in a decolourisation percentage of 70% and 30% for crystal violet and Poly R-478, respectively, after 2 h of treatment. As for the latter, it was not able to degrade Poly R-478, whereas crystal violet reached a degradation of 40% in 2 h.     

Cover crops and natural vegetation mulch effect achieved by mechanical management with lateral rotary mower in weed population dynamics in citrus

The aim of this study was to obtain information on practical weed management in order to reduce the use of herbicides thereby contributing to the sustainable development of citrus crop. The experiment was carried out under field conditions at the experimental area of the Department of Vegetal Production at the College of Agriculture "Luiz de Queiroz," Piracicaba, SP, Brazil, during the season 2002-2003. Influence of mulches produced by four types of vegetations on the dynamic population of weeds in the line of citrus crop (Citrus sinensis (L.) Osbeck) was evaluated. The experimental design was of factorial randomized blocks (4 x 2), where the treatments were: (i) four types of vegetation: Dolichos lablab L., Cajanus cajan (L.) Millsp, Penisetum glaucum (L.) Leeke, and the natural infestation composed basically by Panicum maximum Jacq.; and (ii) two types of fertilization: directed under canopy and broadcast. Mechanical management of the different vegetations was accomplished using a lateral rotary mower, KAMAQ, I model NINJA MAC 260, projected to release the green cut material under crop canopy, forming a mulch layer. The studied parameters were: (i) counting of weeds per m2 in the crop line after 30, 60, 90, 180, and 210 days following the cutting of existing vegetation; (ii) percentage of covered area by weeds; and (iii) some chemical properties of the soil. It was observed that the natural infestation showed a better weed control when compared with the other treatments, and that the broadcast fertilization, regardless of coverage used, presented a lower number of weeds.     

Biodegradation of technical mixtures of oxyethylenated aliphatic alcohols in an aqueous environment

A study of the biodegradability of nonionogenic surfactants of oxyethylenated n-butyl, isobutyl, n-pentyl and isopentyl alcohols was conducted by modified static test according to International Standard Organization method 9888. Degradation was evaluated by changes in concentrations of individual oligomers, ethylene glycols, carboxylic and dicarboxylic acids. Good biological degradability was found, with a "primary" degradability of 75-98% in 10 days. Obtained results, in agreement with our previous work, proved the dominant proportion of degradative scission in the hydrophile part of surfactant molecule. During biological degradation no significant cumulation of mono- to polyethylene glycols appeared neither that of mono- or dicarboxylic acids, and degradation of these components was not a rate-determining degradation factor.     

Importance of considering pesticide stereoisomerism--proposal of a scheme to apply Directive 91/414/EEC framework to pesticide active substances manufactured as isomeric mixtures

An important gap has been detected in the application of the European framework for the evaluation of pesticide active substances constituted by enantiomeric and other kind of stereoisomeric mixtures. Up to date, little attention has been paid to the different biological properties of these compounds. Considering efficacy, toxicity, environmental fate and behaviour and ecotoxicity of separated isomers is necessary to fulfil Directive 91/414/EEC objectives of health and environment protection. Here, a critical review of this question for pesticide active substances is presented. An evaluative scheme for considering this question in the framework of Directive 91/414/EEC is also proposed.     

Isolation and identification of intermediates from biodegradation of low chlorinated biphenyls (Delor-103)

Microorganism Pseudomonas species P2 metabolizes polychlorinated biphenyls (PCBs) and biphenyl, producing the whole spectrum of intermediates, among them coloured intermediates, which are suitable for the monitoring of PCBs degradation by optical sensors. Knowledge of chemical structures and conditions of development of colour metabolites is necessary for application of optical analytical methods. The main goal of this work was the isolation and identification of intermediates from the biodegradation of the mixture of low chlorinated biphenyls (Delor-103), which is based on the solid phase extraction (SPE) of the whole mixture using LiChrolut EN cartridges, then silylation of the extract as one way to the identification of one part of intermediates by GC-MS, and acetylation of the extract as a way for the further concentration and analysis of more polar chlorobiphenylols and chlorobiphenyldiols. The combination of SPE and following acetylation allows to obtain chlorobiphenylols and chlorobiphenyldiols as an almost pure fraction. The acetylation method could be also used instead SPE procedure with the same final concentration effect. Using the simulation mass spectrometry program, two new compounds, dihydrodihydroxytrichloro- and tetrahydrodihydroxytrichlorobiphenyl, as silylderivatives, were identified.     

Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches

The presence of toxic metals on paper pulp and the migration of these metals to food from the food package is receiving significant attention. The final exposure levels for consumers depend on two main processes. First the potential of metals to bind paper pulp during manufacture. Second, the metal potential to migrate from paper to food during storage and use. Binding and unbinding processes are modelled for cadmium kinetics through kinetic approaches. The cadmium concentration in paper pulp is estimated from the cadmium concentration in the water-pulp liquor during manufacture, the temperature, and contact time. Two food simulants have been employed for desorption studies, water and acetic solution (3%, w/w). As expected, under acidic conditions desorption is total and rapid (close to 100% desorption reached in a few minutes). However, the desorption of cadmium into the neutral food simulant depends on the initial cadmium concentration in the paper pulp, temperature and contact time. Surface response curves for each combination are presented. Temperature did not affect cadmium binding, but played a significant role for the desorption processes into the neutral food simulant. The proposed equations offer a good fitting of the experimental values, with p < 0.001 and residuals within a factor of 3 for over 99% of the measured data. These models allow estimations of the expected exposure levels in consumers, on the basis of manufacture and use conditions. Linking the expected exposure with toxicity thresholds, such as the admissible daily intake (ADI), would allow a scientific assessment of the maximum acceptable cadmium levels in water-pulp liquors during manufacture and in the final paper pulp on the basic of the use patterns of each food packaging material.     

Adsorption of atrazine from aqueous solution on heat treated kerolites

The adsorption of 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on heat treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from aqueous solution at 25 degrees C has been studied. The evolution of surface properties of kerolite samples such as specific surface area and porosity after heat treatment was analysed. The clays were characterised by using usual techniques: FTIR spectroscopy, XRD diffraction, TG and DTG analysis, surface analysis and Hg porosimetry. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values range from 468 mgkg(-1) for the K-110 sample up to 2291 mgkg(-1) for the K-600 sample. The values obtained for the removal efficiency (R), (percentage of pesticide removed), ranged from 48% for K-110 up to 78% for K-600. The adsorption experiments showed that the stronger heat treatment, the most effective adsorption of atrazine, so, as this type of clay is relatively plentiful, these activated samples might be used in order to remove this pesticide from water.     

Trypsin inhibitor,antioxidant and antimicrobial activities as well as chemical composition of potato sprouts originating from yellow- and colored-fleshed varieties

Abstract

Potato sprouts could be a valuable resource of phytochemicals such as secondary plant metabolites, potential antioxidants and nutritive compounds. In this work, potato sprout extracts of five varieties were examined; they differed in major glycoalkaloid content, trypsin inhibitor activity, total polyphenol content and antioxidant activity, as well as in antimicrobial activity against Gram?+?and G???bacteria, and yeast. Sprouts of colored-fleshed tubers were characterized by higher trypsin inhibitor activity than sprouts of yellow potatoes. The strongest microorganism growth inhibition effect was observed for macerate with sprouts from the purple-fleshed Blaue Annelise variety against B. subtilis, whereas C. albicans yeasts were sensitive to macerates with sprouts from purple-fleshed Blue Congo and yellow-fleshed Vineta potato varieties.