Effect of temperature on the release and remobilization of ecotoxic elements in AMD colloidal precipitates: the example of the Libiola copper mine, Liguria, (Italy).

Due to their characteristics, colloidal particles are able to control the dispersion of many organic and inorganic pollutants in soils and streams. Colloidal precipitates generated by acid mine drainage (AMD) process are usually amorphous or nanocrystalline materials, and their stability plays a crucial role in controlling the fate of metals released by sulphide oxydation. This paper describes a study of elements release (Fe, Al, Mn, Cd, Co, Cr, Cu, Ni, S, Zn) due to desorption or destabilization of three different colloidal precipitates, two ochreous and a greenish-blue precipitate, sampled at the Libiola mine site (northwest Italy). The samples were heated at high temperature in order to verify this treatment as inertization process. At room temperature, the most easily extracted element was S (with released percentages from 8.39 to 29.17 %), but considerable amounts of Cu, Zn and Mn (up to 16.6, 610.6 and 595.6 mg/kg, respectively) were also observed in the leachates for greenish-blue precipitates. The highest release of elements (S > Cu, Zn, Mn, Cd > Co, Ni > Al, Fe, Cr), with minor differences depending on the mineralogical composition of the samples, was observed for heat-treated samples obtained through moderate heating and mainly formed by anhydrous phases. Samples treated at high temperature had the lowest release, with only Cu showing a significant concentration in the leachate of greenish-blue precipitates. The results showed that dissolution/desorption is limited from ochreous natural colloidal precipitates occurring at the Libiola mine site but also that high amounts of some metals can be remobilized from greenish-blue precipitates. The destabilization of all percipitates through dehydratation-dehydroxylation can further remobilize important amounts of ecotoxic elements. Heat treatment at high temperature could be a definitive, although expensive, way to fix heavy metals in the solid fraction, preventing their dispersion in the surrounding environment.

Preparation and properties of macroporous brushite bone cements.

In the present work a macroporous brushite bone cement for use either as an injected or mouldable paste, or in the shape of preformed grafts, has been investigated. Macropores have been introduced by adding to the powder single crystals of mannitol which worked as a porogen. The size of the crystals was in the range of 250-500microm in diameter, suitable for cell infiltration, with a shape ratio between 3 and 6. From compression tests on cylindrical samples an elastic modulus in the range 2.5-4.2GPa and a compressive strength in the range 17.5-32.6MPa were obtained for a volume fraction of macropores varying between 15 and 0%. Thus the compressive strength exceeded in all tests the maximum value currently attributed to cancellous bone.

Effects of extremely low frequency electromagnetic fields on the adenylate kinase activity of rod outer segment of bovine retina.

Extremely low frequency electromagnetic fields (ELF-EMFs) of 75 Hz with amplitudes above a threshold of about 125 microT have a dramatic effect on the adenylate kinase (AK) activity of the rod outer segment (ROS) membranes. In fact, the ATP production by ROS membranes or by purified disk membranes placed in the field decreased by approximately 54%. The decrease in enzymatic activity was independent of the time of exposure to the field and was completely reversible. When disk membranes were solubilized with Triton or a soluble isoform of AK was used, negligible effects of the field were obtained on the enzymatic activity, suggesting that the membrane has an important role in determining the conditions for the enzyme inactivation.

Electromagnetic field of extremely low frequency decreased adenylate kinase activity in retinal rod outer segment membranes.

Adenylate kinase activity in rod outer segment membranes of bovine retina decreased of about 55% when exposed to an extremely low frequency electromagnetic field of 75 Hz and 250 microT. The effect was independent of the time of permanence in the field. Negligible effects of the field were found on the enzymatic activity of a soluble isoform of adenylate kinase or of rod outer segment membranes solubilized with Triton, suggesting the importance of the membrane in determining the conditions of the enzyme inactivation.

Role of the water matric potential (psi(M)) and of equilibrium water content (EWC) on the water self-diffusion coefficient and on the oxygen permeability in hydrogel contact lenses.

This paper illustrates a new thermodynamic and kinetic model that describes the relationship between the water self-diffusion coefficient, D*(w/g), in hydrogel contact lenses, in terms of water matric potential (psi(M)) and equilibrium water content (EWC). Experimental measurements on commercial contact lenses yield water thermodynamic activity values ranging between 0.996 and 0.999. The corresponding psi(M) matric potential is, respectively, between -8 and -2J/mol at temperature 35 degrees C. Comparison between water self-diffusion coefficients derived in this paper and those suggested by other authors shows that our values are greater (25%-50%) than the previous ones. The impact of this model on the nature of the oxygen permeability, pi, in the lenses has been evaluated and the changes of pi with psi(M) and EWC are predicted and compared with direct experimental measurements. For the contact lenses investigated, the oxygen permeability turns out to be only a quadratic function of equilibrium water content, despite the fact that the fraction of the "free" water molecules can be as high as 50%.

Interfacial effect of extremely low frequency electromagnetic fields (EM-ELF) on the vaporization step of carbon dioxide from aqueous solutions of body simulated fluid (SBF).

Spontaneous processes in an aqueous solution of body simulated fluid (SBF) were monitored in closed vessel for a period of 1 month at 310 K, at atm pressure, and initial pH of 7.2, both with and without exposure to a square pulsed extremely low frequency electromagnetic fields (EM-ELF) of 250 microT, repeated at 75 Hz. The most important findings are that the SBF surface tension (gamma), evaluated under the EM-ELF field, is lower than the corresponding value measured without EM-ELF at any time. Furthermore, the pH of the exposed SBF is always more basic than that of the unexposed solution. As a consequence, when the EM-ELF is applied, calcium phosphate salts do not precipitate from the SBF solution for a period as long as 30 days. Behind all these experimental evidences there is only one mechanism: the vaporisation from the SBF-air interface of the CO(2)(aq) dissolved into the aqueous electrolyte solution. Thermodynamic analysis of these results establish that, at any given time, the difference, Delta, between the measured surface tensions with and without EM-ELF applied, gives the work of the electromagnetic forces to change the extent at which the CO(2)(aq) adsorbs at the liquid-air interface. It has been demonstrated that the work supply per second and per unit of area by the electromagnetic forces, 3.73 x 10(-10) mJ/s cm(2), is very near to the experimental slope in the plot Delta vs. t 1.7 x 10(-10) mJ/s cm(2). This leads to the conclusion that the EM-ELF fields have an interfacial effect on the concentration value of the CO(2) (aq) at the SBF-air interface. Because of that, the EM-ELF field is enhancing the CO(2) vaporisation rate; thus any other steps, which are a consequence of this mechanism, are changing. These results allow explanation of previous experiments concerning the precipitation of calcium carbonate from flowing hydrogen carbonate aqueous solution in the temperature range 353-373 K at a pressure of 0.1 MPa under the effect of static magnetic fields.

Biomimetic PMMA-based bone substitutes: a comparative in vitro evaluation of the effects of pulsed electromagnetic field exposure.

Pulsed electromagnetic fields (PEMFs) are known to be effective in the stimulation of cultured osteoblasts and in vivo healing of delayed and nonunion fractures. In the present in vitro study the effects of PEMFs on osteoblastic cell cultures (MG63 human osteoblast-like cells) grown in the presence of poly-methylmethacrylate (PMMA) and of a biomimetic bone substitute made of a PMMA matrix added with alfa-tricalcium phosphate (PMMA+alpha-TCP) were evaluated, to assess the biological response at the cell-biomaterial interaction. Cultures were stimulated with PEMFs (75 Hz, 2.3 mT, 1.3-ms pulse duration) 12 h/day for 3 days and evaluations (MTT, ALP, OC, PICP, TGFbeta-1, IL-6) were performed at 3 and 6 days. PMMA had a negative effect on osteoblasts, whereas PMMA+alpha-TCP enhanced production of ALP, PICP, OC and TGFbeta-1, and reduced IL-6 levels. Cells responded positively to PEMF stimulation even when cultured with a poorly biocompatible material, such as PMMA. This effect was more evident in the presence of PMMA+alpha-TCP (further improvement in proliferation and synthetic activity) both at 3 and at 6 days. The properties of PMMA+alpha-TCP look promising, and the present results support the use of PEMFs to improve tissue response to biomaterials implanted as bone substitutes.

Alpha-tricalcium phosphate hydrolysis to octacalcium phosphate: effect of sodium polyacrylate.

Alpha-Tricalcium phosphate (alpha-TCP) hydrolysis into octacalcium phosphate (OCP) has been investigated in phosphoric acid solution at different concentrations of sodium polyacrylate (NaPA). The hydrolysis process has been followed by powder X-ray diffraction, infrared absorption and scanning electron microscopy analyses. In the absence of the polyelectrolyte, alpha-TCP undergoes a complete transformation into OCP in 24 h. The presence of polyacrylate in solution inhibits the hydrolysis so that a NaPA concentration of 0.5 microm is sufficient to lengthen the time required to complete the hydrolysis to 4 days. The variation of Ca2+ concentration in the soaking solution suggests that the transformation occurs through alpha-TCP dissolution followed by OCP precipitation. The delayed OCP nucleation and growth in the presence of polyacrylate implies a preferential adsorption of the polyelectrolyte on the growing OCP crystals, which induces an anisotropic reduction of the coherence lengths of the perfect crystalline domains.

Use of alpha-tricalcium phosphate (TCP) as powders and as an aqueous dispersion to modify processing, microstructure, and mechanical properties of polymethylmethacrylate (PMMA) bone cements and to produce bone-substitute compounds.

Addition of tricalcium phosphate (alpha-TCP) powders as an aqueous dispersion to a polymethylmethacrylate (PMMA) bone cement is shown to produce a class of composites that due to their microstructure and mechanical properties may be suitable for application as bone substitutes. The PMMA forms a solid cellular matrix with open cells about 100 micrometer in size and incorporating TCP clusters. The TCP aggregates inside the cells form a porous network, with average mesopore diameters of about 0.1 micrometer, that is accessible from the outer surface. If TCP is added to PMMA in the form of dried powders, the composites are not applicable as bone substitutes. The dynamic elastic modulus (DEM) and compressive and tensile strengths were measured and discussed for both classes of composites. The mechanical properties of the bone-substitute composites, although lower than the other class of composites, are still competitive with those properties of a porous ceramic matrix of hydroxyapatite and with those of natural bones.

Franck-Condon Factors for the Ionization of H2O and D2O.

Franck-Condon factors have been calculated for vertical transitions of H2O and D2O involving both bond length and angle changes. It is shown that even in the harmonic oscillator approximation different Franek-Condon factors are obtained for positive and negative angle changes. The results are used to obtain the geometry of the ion ground state. Satisfactory agreement is obtained for the isotope effect on the vibrational transition probabilities. The effects of anharmonicity are discussed semi-quantitatively.