Fat properties during homogenization, spray-drying, and storage affect the physical properties of dairy powders.

Changes in fat properties were studied before, during, and after the drying process (including during storage) to determine the consequences on powder physical properties. Several methods were combined to characterize changes in fat structure and thermal properties as well as the physical properties of powders. Emulsion droplet size and droplet aggregation depended on the homogenizing pressures and were also affected by spray atomization. Aggregation was usually greater after spray atomization, resulting in greater viscosities. These processes did not have the same consequences on the stability of fat in the powders. The quantification of free fat is a pertinent indicator of fat instability in the powders. Confocal laser scanning microscopy permitted the characterization of the structure of fat in situ in the powders. Powders from unhomogenized emulsions showed greater free fat content. Surface fat was always overrepresented, regardless of the composition and process parameters. Differential scanning calorimetry melting experiments showed that fat was partially crystallized in situ in the powders stored at 20 degrees C, and that it was unstable on a molecular scale. Thermal profiles were also related to the supramolecular structure of fat in the powder particle matrix. Powder physical properties depended on both composition and process conditions. The free fat content seemed to have a greater influence than surface fat on powder physical properties, except for wettability. This study clearly showed that an understanding of fat behavior is essential for controlling and improving the physical properties of fat-filled dairy powders and their overall quality.

Preparation and characterisation of raw chars and physically activated carbons derived from marine Posidonia oceanica (L.) fibres.

Industrial valorisation of low cost and renewable biomass as raw precursor of activated carbon for environmental applications is an interesting alternative to costly commercial activated carbons. In this study, the possible use of Mediterranean, Posidonia oceanica fibrous biomass, as a precursor for chars and physically activated carbons, is investigated. Firstly, the raw marine material was chemically and biochemically characterised throughout dry-basis elemental, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis. Then, several P. oceanica chars were prepared and characterised under different pyrolysis times and temperatures. In addition, physically activated carbons (PACs) were produced via water steam flow under various activation periods. The results showed that the pyrolysis induces the creation of pores at different levels with respect to the involved temperature. Thereafter, the physical activation tends to enhance the development of the porous structure. In that issue, the performed Brunauer-Emmett-Teller (BET) and Barrett-Joiner-Halenda (BJH) analysis revealed that the prepared PACs have a mainly mesoporous inner morphology with a varying fraction of micropores.

Adsorption studies of recalcitrant compounds of molasses spentwash on activated carbons.

Due to high levels of residual chemical oxygen demand (COD) in the effluent of molasses spentwash (MSW) after anaerobic treatment, acceptable COD levels for discharge cannot be achieved without some form of post-treatment. In this study, the particulate composition of molasses spentwash after anaerobic digestion (MSWD), is characterised as to its particle size distribution, using micro- and ultrafiltration and three activated carbons are characterised as to their ability to reduce significantly the COD of MSWD effluent. The activated carbons tested as adsorbent, were characterised by XPS spectroscopy, elemental analysis, surface area, pore size distribution, and acid-base titration using the Boehm's method. Adsorption of phenol, used here as a reference compound, and of some organic compounds contained in MSWD (gallic acid, tannic acid, and melanoidin, respectively), was studied. It was clearly demonstrated that an activated carbon with a significant distribution of both micropores and mesopores and a significant amount of macropores that are assumed to act as conduits providing access to micro- and mesopores, have a good adsorption efficiency for compounds such as tannic acid and melanoidins. It is a good adsorbent for melanoidin and coloured compounds of MSWD, which represents a large source of the aqueous pollution in sugar cane industries.

Surface composition of dairy powders observed by X-ray photoelectron spectroscopy and effects on their rehydration properties.

The surface composition of three dairy powders was investigated by X-ray photoelectron spectroscopy. These spray-dried casein powders were more or less enriched in hygroscopic material (lactose and/or minerals). The principal limitation of these high protein content powders is their poor rehydration ability. Consequently, information about surface composition is required in order to get a better understanding of rehydration behaviour (i.e. wetting time and time of rehydration). The obtained results indicate that the surface of the three powders was dominated by proteins. Lactose and minerals are marginal compounds at the surface whereas the surface coverage of fat was over represented. A correlation between the lactose surface content and the wetting time of the powders was found, but no relationship with the surface fat. Moreover, as the surface is partly depleted in minerals and lactose, it is concluded that these compounds are principally located in the bulk of the particle. Therefore this observation could be related with a wetting time of the powders only slightly affected by the addition of hygroscopic material whereas the time of rehydration was strongly improved; powder wetting being more affected by the surface composition whereas powder dispersion being more influenced by the powder bulk composition.

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Sorption of uranium (VI) species on zircon: structural investigation of the solid/solution interface.

This work is an investigation of the mechanisms of interaction between uranium (VI) ions and zirconium silicate. The speciation of uranium (VI) sorbed on zircon was studied using four complementary techniques as probes of the local structure around the uranium atom: laser spectrofluorimetry, X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier-transformed (DRIFT) spectroscopy, and EXAFS spectroscopy. The sorption of uranyl on zirconium oxide was also studied to allow structural comparisons. Spectrofluorimetry and XPS results allowed an identification of the silicate sorption sites on the solid. These methods associated with spectrofluorimetry and DRIFT led to a characterization of the sorbed surface complexes, taking into account the influence of the nature of the background salt and of the pH on the structure of the U(VI) surface species. EXAFS measurements, either on air-dried samples or in situ, were then carried out on well-characterized samples and allowed identification of the sorption mechanism on zircon as the formation of an inner-sphere polydentate surface complex.

Behavior of hexavalent chromium in a polluted groundwater: redox processes and immobilization in soils.

This work describes the chemical mechanisms governing transport and reduction of hexavalent chromium in soils of a contaminated industrial waste landfill. Groundwater and soil analyses indicate that the main source of chromium is a slag heap essentially consisting of mill tailings. In the groundwater, downstream migration of Cr(IV) is limited thanks to a redox mechanism involving chromate ions and ferrous ions or Fe(II)-bearing minerals. High Fe2+ concentrations in the groundwater are a result of pyrite residues from old activities at the site. Analyses of soil samples reveal that chromium is preferentially located in the soil profile at the fluctuation of the groundwater level. Grain size fractionation of four soil samples was performed, and fraction analyses show that chromium is preferentially accumulated in the clay fraction (<2 microm) and more specifically associated with montmorillonite particles. This work is a demonstration of the reduction of Cr(VI) by Fe(II) studied previously in the laboratory (Buerge, I. J.; Hug, S. J. Environ. Sci. Technol. 1997, 31, 1426-1432; Fendorf, S. E.; Li, G. Environ. Sci. Technol. 1996, 30, 1614-1617; Sedlak, D. L.; Chan, P. G. Geochim. Cosmochim. Acta 1997, 11, 2185-2192) in a field setting. Cr(VI) migration into the groundwater is stopped vertically by the very thick green clay unit and horizontally by the presence of Fe(II) acting as a chemical barrier. The specific site conditions safely prevent any extension of the Cr pollution.