Study of metal fractionation in river sediments. A comparison between kinetic and sequential extraction procedures

The extraction kinetic of trace metals (Cd, Cu, Pb, and Zn) in river sediments by four extraction agents was studied. As extractants ammonium acetate, acetic acid, hydroxylamine and EDTA solutions were assayed. These reagents can leach the metals more or less selectively from several metal compartments of sediments. The metal leaching kinetic model permits classification of the metal species in labile and moderately-labile ones. The combination of two or more non specific reagents permits a high characterisation of metal distribution and leachability. The results obtained with this model in four river sediments were compared with data obtained by the SM&T sequential extraction procedure, in order to characterise the chemical nature of leached metal.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

Contribution of LPG-derived emissions to air pollution in the metropolitan area of Guadalajara City

Measurements of hydrocarbon (HC) emissions generated by the use of liquefied petroleum gas (LPG) in the metropolitan area of Guadalajara City (MAG) are presented in this work. Based on measurements in the course of distribution, handling, and consumption, an estimated 4407 tons/yr are released into the atmosphere. The three most important contributors to LPG emissions were refilling of LPG-fueled vehicles and commercial and domestic consumption. The MAG shows a different contribution pattern of LPG emission sources compared with that of the metropolitan area of Mexico City (MAMC). These results show that each megacity has different sources of emissions, which provides more accurate strategies in the handling procedures for LPG to decrease the impact in O3 levels. This work represents the first evaluation performed in Guadalajara City, based on current measurements, of the LPG contribution to polluting emissions.     

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.     

Empty nests in the great tit (Parus major) and the pied flycatcher (Ficedula hypoleuca) in a polluted area

Great tits (Parus major) are sometimes found to incubate in their nests even though the nests contain no eggs. This phenomenon has been observed in different parts of Europe (Sweden, Finland, UK, Netherlands, Germany) and it has become more common during the 1980s. We analysed the occurrence of empty nests in P. major and in pied flycatcher (Ficedula hypoleuca) in SW Finland from 6-year data collected in a polluted area around a copper smelter which emits large quantities of sulphuric oxides and heavy metals. Among first broods 3.3% of P. major females incubated in empty nests. Incubation on empty nests was not observed in F. hypoleuca, but in this species 2.4% of the nests remained without eggs. In both species empty nests were more common close to the pollution source than farther away. Histopathological analyses in P. major suggest that there are diverse reasons for the incapability of a female to lay. One out of five P. major females captured from incubating in an empty nest had dark cysts in her oviduct. Two P. major females had very scanty medullary bone tissue in their tibiotarsus and tarsometatarsus and one female showed exceptionally high concentrations of lead in her bone tissue. We conclude that air pollutants enhance the number of empty nests especially in F. hypoleuca, but cannot wholly explain the phenomenon in P. major.     

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.