Chemical variability of artificial stone powders in relation to their health effects.

The occurrence of highly severe silica-related diseases among the resin- and silica-based artificial stone workers was claimed, associated to an extremely short latency. High levels of exposure and intrinsic properties of AS are thought to modulate the development of silicosis and auto-immune diseases. This study compares parent materials and processed dusts, to shed light on changes of AS occurring in the manufacturing process, through an XRF, EPR and XAS investigation. We point out the extremely wide variability of the materials, the occurrence of chemical signatures impressed by the processing techniques, and the unprecedented generation of stable radicals associated to the lysis of the Si-O chemical bond inside the resin coated respirable crystalline silica. These results suggest that the AS processing in industrial stone workshops can create respirable dusts with peculiar physical and chemical properties, to be correlated to the observed clinical evidences.

Thallium-rich rust scales in drinkable water distribution systems: A case study from northern Tuscany, Italy.

Following the detection of a severe thallium contamination of the drinkable water from the public distribution system of Valdicastello Carducci-Pietrasanta (northern Tuscany, Italy), and the identification of the source of contamination in the Molini di Sant'Anna spring (average Tl content≈15µgL-1), the replacement of the contaminated water with a virtually Tl-free one (Tl<0.10µgL-1) caused an increase in Tl concentration in the drinkable water. This suggested that the pipeline interior had become a secondary source of Tl contamination, promoting its mineralogical and geochemical study. Rust scales samples taken from several pipeline segments, as well as leaching products obtained from these samples, were investigated through scanning electron microscopy, X-ray fluorescence chemical analyses, inductively coupled plasma - mass spectrometry, X-ray diffraction, and X-ray absorption spectroscopy. Thallium-rich rust scales (up to 5.3wt% Tl) have been found only in pipeline samples taken downstream the water treatment plant, whereas the sample taken upstream contains much less Tl (~90µgg-1). The Tl-rich nature of such scales is related to the occurrence of nano- and micro-spherules of Tl2O3 and less abundant nanocrystalline µm-sized encrustations of TlCl. Leaching experiments on Tl-rich rust scales indicate that a fraction of the available Tl is easily dissolved in tap water; X-ray absorption spectroscopy suggests that monovalent thallium occurs in water equilibrated with the rust scales, probably related to the dissolution of TlCl encrustations. Therefore, Tl dissolved as Tl+ only in the water from the Molini di Sant'Anna spring was partially removed through oxidative precipitation of Tl2O3 and precipitation of TlCl. This highlights the critical role played by the addition of chlorine-based oxidants in water treatment plants that could favour the deposition of Tl-rich coatings within the pipelines, giving rise to unexpected secondary sources of contamination.