Vincent Gloaguen

HEAVY METAL ADSORPTION BY CRUDE CONIFEROUS BARKS: A MODELLING STUDY

ABSTRACT Equilibria and mechanisms involved in the adsorption process of metal ions (Cr3+, Cu2+, Ni2+, Pb2+ and Zn2+) from aqueous solutions using coniferous barks as biosorbent substrate were investigated. Crude barks were used in this study since previous experiments showed a decreasing uptake for chemically treated barks in the considered granulometry. In our experimental conditions, the maximum binding capacity of barks followed the decreasing order Cr3+>Cu2+>Pb2+>Ni2+>Zn2+ whereas their general binding affinity decreased as: Pb2+>Cr3+> Ni2+>Zn2+>Cu2+. Adsorption isotherms at the optimal physico-chemical conditions were established and the adsorption phenomenon was described by the non-competitive Langmuir adsorption model which fitted well the experimental data. An evaluation of adsorption capability was carried out using model parameters which were graphically determined. Models for removal of cations have been discussed; they represent efficient tools for predicting the behaviour of the biosorbents in metal ion adsorption systems.

Removal of heavy metal ions from aqueous solution by modified barks

Abstract Bark, a common waste product in forestry, can be used to selectively remove cations, especially toxic heavy metals from mono or multi saline solutions. Picea, Pinus, Pseudotsuga, Larix, Tectona and Afzelia barks have been used in glass columns, after grinding and treatment with formaldehyde in acid media, to study their ability in binding toxic heavy metal ions such as Pb2+, Zn2+, Cr2+, Fe2+ and Cu2+. The metals are exchanged against protons on the bark substrates that presumably contain carboxyl groups in both pectin and tannin compounds. Removal of these ions depends upon the nature of the bark used, the grain size and the predominant heavy metal ions present in the solutions. The metal ions could be stripped by addition of 0.1 ? HCl, making the substrate regeneration and its reutilization possible.

Properties of cellulosic fibre reinforced plaster: influence of hemp or flax fibres on the properties of set gypsum

In the last few years, eco friendly materials have become an important part of the building materials market. Natural fibres are already used in various types of materials, like plastics, concrete and lime-based products. They demonstrate different attributes like the combination of good mechanical, thermal and acoustic properties that allow these types of materials to be used for different applications. The main drawback associated with plaster is its brittleness, especially under tensile stress. Therefore, it is interesting to investigate different methods that could potentially enhance the mechanical properties of plaster. Adding fibres to gypsum to obtain a composite material is one way to improve the behaviour of the product, especially after the failure of the matrix. The aim of this work was to the study the effects of adding natural fibres, namely hemp and flax fibres, on the setting time of plaster and the mechanical properties of the composite matrix. It was shown that hemp delayed the setting of plaster, unlike flax. The initial and final setting times almost doubled when hemp was added in a plaster matrix, whereas flax fibres did not drastically change them. Different chemical treatments of hemp were tested and the impact on the setting time was measured. The setting times of both composites made with hemp and flax were reduced once the fibres were treated (25–40% reduction), compared to the setting time of the calcium sulphate hemihydrate alone. The mechanical properties of the composite materials are also discussed. The behaviour of plaster was modified from brittle to a non-linear one when fibres were added, and even at small levels of addition, flax fibres allowed slightly higher values of flexural strength to be reached.

Anti-inflammatory and immunological effects of Centaurea cyanus flower-heads

Centaurea cyanus flower-heads are used in European phytotherapy for the treatment of minor ocular inflammations. Different pharmacological experiments (inhibition of carrageenan, zymosan and croton oil-induced oedemas, inhibition of plasma haemolytic activity, induction of anaphylatoxin activity) showed that polysaccharides extracted from C. cyanus flower-heads had anti-inflammatory properties and interfered with complement. Moreover, these polysaccharides were found to be mainly composed of galacturonic acid, arabinose, glucose, rhamnose and galactose.

Study of the Chemical Interaction between Barks and Heavy Metal Cations in the Sorption Process

The chemical mechanism displayed in the sorption of heavy metal cations on barks was discussed through a modelling study of adsorption in relation to the nature of the ligand borne by the chemical components of the bark sorbent. The adsorption isotherms of five heavy metal cations (Cr3 +, Cu2 +, Ni2 +, Pb2 +, Zn2+) on five species of barks (Sweet chestnut, Oak, Douglas fir, Norway spruce, Scots pine species) were studied. The experimental data fitted well the Langmuir model, which allowed the expression of the mathematical parameters (q max, maximum binding capacity; b, affinity). The q max values increased conversely to the b values. The correlation of these mathematical values (q max and b) with the analysis of the chemical composition of barks led us to note that Cu2 + interacts preferentially with phenolic groups present in lignins and tannins and, opposite in, Pb2 + with the carboxylic acid groups in polysaccharides. These observations were explained (i) quantitatively by the amount of different types of sites and (ii) qualitatively, by the physicochemical characteristics of cations, the nature and the tridimensional structure of adsorption sites. Finally, the results allowed to define the nature of the chemical interaction (monodentate or multidentate complex) between each specified chemical component of barks and each kind of heavy metal cations.

Structural Characterization and Cytotoxic Properties of an Apiose-Rich Pectic Polysaccharide Obtained from the Cell Wall of the Marine Phanerogam Zostera marina

Zosterin, an apiose-rich pectic polysaccharide, was extracted and purified from the sea grass Zostera marina. Structural studies conducted by gas chromatography and NMR spectroscopy on a purified zosterin fraction (AGU) revealed a typical apiogalacturonan structure comprising an alpha-1,4-d-galactopyranosyluronan backbone substituted by 1,2-linked apiofuranose oligosaccharides and single apiose residues. The average molecular mass of AGU was estimated to be about 4100 Da with a low polydispersity. AGU inhibited proliferation of A431 human epidermoid carcinoma cells with an approximate IC(50) value of 3 microg/mL (0.7 microM). In addition, AGU inhibited A431 cell migration and invasion. Preliminary experiments showed that inhibition of metalloproteases expression could play a role in these antimigration and anti-invasive properties. Autohydrolysis of AGU, which eliminated apiose and oligo-apiose substituents, led to a virtual disappearance of cytotoxic properties, thus suggesting a direct structure-function relationship with the apiose-rich hairy region of AGU.

Chemical Valorization of Forest and Agricultural By-Products. Obtention, Chemical Characteristics, and Mechanical Behavior of a Novel Family of Hydrophobic Films

Abstract Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity—resistance to traction ratio.

Inhibition of Croton Oil-Induced Oedema in Mice Ear Skin by Capsular Polysaccharides from Cyanobacteria

Abstract. The anti-inflammatory properties of hydrophilic extracts of the capsular polymers of twelve cyanobacterial strains belonging to the genera Phormidium and Nostoc from marine and terrestrial habitats were tested topically on croton oil-induced oedema in mice ear skin. The screening program identified several strains as producers of anti-inflammatory products (up to 56% inhibition of the oedema). The inhibition response was dose-dependent. The application of trichloroacetic acid-treated extracts reduced the oedema by about 60%. On the other hand, one of the strains enhanced the inflammatory response.Analysis of five of the extracts showed the presence of neutral sugars (from 34.3% to 47.1%, w/w), uronic acids (from 7.1% to 26.7%, w/w) and proteins (from 30.1% to 57.0%, w/w) in the crude polymer. Rhamnose, fucose, arabinose, xylose, mannose, glucose, galactose, galacturonic acid and glucuronic acid were detected as well as sulphate groups (from 9.6% to 21.5%, w/w of sugars). The main components found were glucose and mannose.

Capsular polysaccharides secreted by building façade colonisers: characterisation and adsorption to surfaces

Abstract Exopolymers secreted by algal and cyanobacterial strains isolated from building façades were imaged by microscopy techniques. They were extracted and characterised to investigate their possible contribution to interactions with solid surfaces. The polymers were polysaccharides, with anionic and hydrophobic properties varying between the various strains. Capsular polysaccharides extracted from a strain of Klebsormidium flaccidum adsorbed in higher amounts on hydrophobic than on hydrophilic surfaces. These results tend to confirm the hypothesis that exopolymers are important in the colonisation process of microorganisms to surfaces.

Metal accumulation by immobilized cyanobacterial mats from a thermal spring

Abstract The metal‐binding properties of lyophilized cyanobacterial mats occurring in a thermal spring were investigated. The general binding efficiency decreased in the order Cu > Ni > Pb > Cr. Most metal sorption occurred within 15 min, and it was strongly pH‐dependent. The sorption of Cu was depressed in the case of competition with other metals or cations. The metal‐binding properties are probably due to a high density of anionic charges, especially carboxyls, identified in the capsular polymer. The feasability to use columns packed with the biomass immobilized with silica gel for the removal of metals is demonstrated. The metals were successfully desorbed and these columns were effective during several adsorption‐desorption cycles.