Unlikely lead-bearing phases in river and estuary sediments near an ancient mine (Huelgoat, Brittany, France).

Anthropocene mineral diversity is the result of the purification of metals naturally combined with other chemical elements in natural environment. Moreover, the advent of human mining and manufacturing mineral-like compounds has experienced a punctuation event in diversity and distribution owing to the pervasive impact of human activities. In this context, the wastes of an abandoned historical mine, Huelgoat mine (Brittany, France), famous during the eighteenth and the nineteenth century contain significant amounts of chemical elements potentially dangerous to the environment. Lead concentration and Pb-bearing phases were quantified in 7 sediments samples located from mine upstream to the Aulne estuary (100 km downstream to the mine). Results show very high concentrations of lead in the stations located upstream and downstream of the Huelgoat mine, using X-ray fluorescence spectroscopy, ranging from 7000 mg/kg downstream of the mine to a natural concentration of about 80 mg/kg upstream. At the same time, Pb-bearing phases were identified depending on the particle sizes, fine (< 50 µm) and coarse (> 50 µm), using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), total organic carbon (TOC), and pH analyses. For the first time, evidence of anthropogenic mineral "iodoplumbate" formation has been described in a natural environment.

3D optical detection in radiodosimetry: EasyDosit hydrogel characterization.

In this study the spectrophotometric behaviour of gelatin-based hydrogels, in the presence and absence of dyes, was studied. The aim was to formulate equivalent-tissue phantoms to be used as 3D-dosimeter, suitable for Optical Computed Tomography (OCT). The hydrogels show good transparency and good stability of baseline optical density and, in the presence of dye, the response of optical density as a function of concentration was higher than in aqueous solution. The hydrogels were formulated in order to reduce the diffusion of the image of the irradiated field over time and to have stable fantoms as a function of time. To this purpose, the diffusion coefficients of two dyes, Bromophenol Blue (BPB) and Bromocresol Green (BCG), were determined as a function of the hydrogel chemical composition. As comparison, in some experiments Xylenol Orange (XO) was used. In particular, the presence of sucrose, as thickener, can reduce to almost half BPB mobility. In conclusion, it was shown that optical properties and controlled dye diffusion in gelatin-based hydrogels could allow using them as 3D-dosimeter for optical detection.

Hydroxyapatite precipitation with Hydron Blue dye.

Calcium phosphate, in the form of amorphous hydroxyapatite, precipitates out of neutral water solutions containing calcium and phosphate ions in the form of small agglomerates of 18 µm average size. When Hydron Blue dye (HB) is added, the insoluble particles gradually agglomerate further to 50 µm sizes. However, the removal capacity of hydroxyapatite for the dye is increased when the calcium phosphate nucleates and forms in the presence of dye. When coprecipitates form, the particules average 20 µm size and contain up to 60% organic matter. Nascent calcium phosphate particles have strong capacity for Hydron Blue dye removal. Thus smaller calcium phosphate particles increase the amount of dye molecules in water pollution control.

Hazardous animal waste carcasses transformation into slow release fertilizers.

Because of the need to address disposal of materials infected with pathogens new regulations have come into effect for the transport and disposal of dead farm animals or carcasses. For precautionary reasons, disposal to landfill, composting, biogas generation or fertilizer use are banned recycling paths because of incomplete knowledge about contamination transmission paths. Thermal treatment is recognized as a safe elimination process. Animal wastes have a high calorific value (above 16 MJ/kg). However, combustion of the organics leaves mineral residues (near 30%). The ashes contain mostly calcium and phosphate with some sodium, potassium and magnesium. We have examined the transformation of the ashes into a slow release fertilizer. We used a mixture of acids to partly dissolve the combustion residues and form slurry. In a second step, base was added to neutralize and solidify the reaction mixture. The final product was a whitish polycrystalline solid. Leaching tests were made to evaluate the nutrient release rate in laboratory columns. Water leachates were analyzed for up to ten pore-bed volumes and showed, as expected, large differences in release rates. Nitrate release was slowed and phosphate did not level even after ten pore-bed volumes. This demonstrates that insoluble precipitates (gypsum) contribute to control soluble ion release.

Copper(II) interactions with non-steroidal anti-inflammatory agents. III--3-Methoxyanthranilic acid as a potential *OH-inactivating ligand: a quantitative investigation of its copper handling role in vivo.

Pharmacological activities of copper(II) complexes are a direct function of the nature of their ligands associated with the metal ion in vivo. Some of these, defined as *OH-inactivating ligands (G. Berthon, Agents Actions 39 (1993) 210-217), may act as specific "lures" for hydroxyl radicals at inflammatory sites and behave as pseudo-catalase-like agents. This property has been advanced for anthranilic acid (H. Miche, V. Brumas, G. Berthon, J. Inorg. Biochem. 68 (1997) 27-38). With a view to improve the chemical features required to render such inactive substances effective anti-inflammatory drugs through their association with copper(II), an in vitro investigation into copper(II) interactions with the anionic form of an anthranilic acid derivative, namely 3-methoxyanthranilate (Man), has been performed under experimental conditions pertaining in vivo. Copper(II)-Man complex equilibria have been determined using glass electrode potentiometry, then checked by UV-vis and mass spectrometries. Given the prime role of histidine as a copper(II) ligand in blood plasma, copper(II)-histidine-Man ternary equilibria have also been studied. Subsequent computer simulations of the distribution of copper(II) in the extracellular fluid revealed that Man can specifically mobilize Cu(II) ions under inflammatory conditions without affecting their distribution under normal physiological conditions. Thiobarbituric acid reactive substances (TBARS) tests conducted with respect to standardized copper-mediated Fenton-type reactions (P. Maestre, L. Lambs, J.P. Thouvenot, G. Berthon, Free Rad. Res. 20 (1994) 205-218) have shown that, like anthranilic acid, Man can effectively both increase the Fenton-like reactivity of copper and decrease the amount of TBARS detected in solution, i.e., act as a potential *OH-inactivating ligand.

Release of anthracyclines adsorbed on copper-treated hydroxylapatites.

Anthracyclines are antibiotics widely used for the treatment of leukemia and solid tumors. Perfusion is the standard clinical administration form. Unfortunately, this does not allow treatment of gastric cancers. A new galenic presentation, consisting of anthracyclines adsorbed onto hydroxylapatite granules, has been developed. It was found to be possible to modulate the release of the drug as a function of the pH by using copper(II) ions. At neutral pH, the drug remains on the mineral support, but at pH 3, the drug is released into solution. Further investigations demonstrate that copper-containing hydroxylapatite can retain a determined quantity of antibiotic by surface complexation. This result could contribute to new designs for drug carriers targeted for gastric cancers.

Mitomycin antitumor compounds. 2. Interaction of transition metal ions with mitomycin C. Solution structure and biological activity of a Pd(2+)-MMC complex.

Interactions of Cu(2+), Zn(2+), and Pd(2+) ions with the antitumor compound mitomycin C (MMC) have been investigated by UV-vis, circular dichroism, and (13)C NMR spectroscopy. While Zn(2+) and Cu(2+) neither interacted with MMC nor catalyzed the formation of mitosenes, Pd(2+) induced strong MMC spectral modifications, suggesting the formation of a major complex, in which MMC acted as a bidentate ligand through N(1) and N(4) atoms. The coordination mode in this complex was solvent dependent: in MeOH, the NH(2) of the carbamate function was also involved as a third coordination site whereas, in H(2)O, Pd(2+) hydrolysis was more effective, leading to the replacement of the carbamoyl NH(2) function with either H(2)O or OH(-) ligands. Although coordination of the indoline nitrogen prevented methanol elimination and consequent aziridino ring opening, Pd(2+) complexation maintained MMC biological activity against cancer cells, as shown by IC(50) values. This suggests that alternative mechanisms in the biological activity of MMC should be explored.

Interactions of the anticancer antibiotic altromycin B with copper(II), palladium(II) and platinum(II) ions and in vitro activity of the formed complexes.

Interaction of the anticancer antibiotic altromycin B with Cu(II), Pd(II) and Pt(II) ions was studied using 1H-NMR, EPR, electronic absorption and circular dichroism spectroscopy. The results derived from NMR studies where that the Pt(II) and Pd(II) ions interact with the nitrogen atom of the dimethylamino group of the C(10)-disaccharide, while the C(2)-epoxide group does not participate and remains intact. Cu(II) ions interact in a different way with altromycin B as was concluded by EPR and circular dichroism spectra. Altromycin B coordinates to the Cu(II) ions via the oxygen atoms of the C(11) phenolic and the C(12) carbonyl group while the nitrogen atom does not participate in the complexation. The presence of these metal ions improves the stability of altromycin B in solution. These complexes were studied in vitro against K562 leukemia sensitive and doxorubicin-resistant cells and GLC4 lung tumor cells, sensitive and doxorubicin-resistant. The activity of the complexes compared to the free drug is improved against resistant cells and is affected moderately against sensitive cells. Finally, 20% of platinum added as altromycin B metal complex entered GLC4 cells.