Magdalena Lassinantti Gualtieri

Recycling of the product of thermal inertization of cement-asbestos for various industrial applications

Recycling of secondary raw materials is a priority of waste handling in the countries of the European community. A potentially important secondary raw material is the product of the thermal transformation of cement-asbestos, produced by prolonged annealing at 1200-1300 °C. The product is chemically comparable to a Mg-rich clinker. Previous work has assured the reliability of the transformation process. The current challenge is to find potential applications as secondary raw material. Recycling of thermally treated asbestos-containing material (named KRY·AS) in traditional ceramics has already been studied with successful results. The results presented here are the outcome of a long termed project started in 2005 and devoted to the recycling of this secondary raw materials in various industrial applications. KRY·AS can be added in medium-high percentages (10-40 wt%) to commercial mixtures for the production of clay bricks, rock-wool glasses for insulation as well as Ca-based frits and glass-ceramics for the production of ceramic tiles. The secondary raw material was also used for the synthesis of two ceramic pigments; a green uvarovite-based pigment [Ca(3)Cr(2)(SiO(4))(3)] and a pink malayaite-based pigment [Ca(Sn,Cr)SiO(5)]. The latter is especially interesting as a substitute for cadmium-based pigments. This work also shows that KRY·AS can replace standard fillers in polypropylene plastics without altering the properties of the final product. For each application, a description and relevant results are presented and discussed.

The zeta potential of mineral fibres

For the first time, the zeta (ξ) potential of pathogenic mineral fibres (chrysotiles, amphiboles and erionite) was systematically investigated to shed light on the relationship between surface reactivity and fibre pathogenicity. A general model explaining the zeta potential of chrysotile, amphiboles and erionite has been postulated. In double distilled water, chrysotiles showed positive values while crocidolite and erionite showed negative values. In contact with organic solutions, all fibres exhibited negative values of zeta potential. The decrease of the surface potential is deemed to be a defensive chemical response of the macrophage cells to minimize hemolytic damage. Negatively charged surfaces favour the binding of collagen and redox activated Fe-rich proteins, to form the so-called asbestos bodies and prompt the formation of HO via the reaction with peroxide (H2O2+e(-)→HO+HO(-)). An additional mechanism accounting for higher carcinogenicity is possibly related to the Ca(2+) sequestration by the fibres with surface negative potential, impairing the mitochondrial apoptotic pathway. It was also found that with a negative zeta potential, the attractive forces prevailed over repulsions and favoured processes such as agglomeration responsible of a tumorigenic chronic inflammation.

Ambient monitoring of asbestos in selected Italian living areas

This paper presents the results of an intensive monitoring activity of the particulate, fall-out and soil of selected living areas in Italy with the aim to detect the asbestos concentration in air and subsequent risk of exposure for the population in ambient living environments, and to assess the nature of the other mineral phases composing the particulate matrix. Some areas were sorted out because of the presence of asbestos containing materials on site whereas others were used as blank spots in the attempt to detect the background environmental concentration of asbestos in air. Because the concentration of asbestos in ambient environments is presumably very low, and it is well known that conventional low-medium flow sampling systems with filters of small diameter (25mm) may collect only a very small fraction of particulate over a short period, for the first time here, an intense monitoring activity was conducted with a high flow sampling system. The high flow system requires the use of large cellulose filters with the advantage that, increasing the amount of collected dust, the probability to collect asbestos fibers increases. Both the protocol of monitoring and analysis are novel and prompted by the need to increase the sensitivity towards the small number of expected fibers. With this goal, the collection of fall-out samples (the particulate falling into a collector filled with distilled water during the monitoring shift) and soil samples was also accomplished. The analytical protocol of the matrix particulate included preliminary X-ray powder diffraction (XRPD), optical microscopy and quantitative electron microscopy (SEM and TEM). Correlations with climatic trends and PM10 concentration data were also attempted. The surprising outcome of this work is that, despite the nature of the investigated site, the amount of dispersed asbestos fibers is very low and invariably lower than the theoretical method detection limits of the SEM and TEM techniques for identification and counting of asbestos fibers. The results are compared to the literature data worldwide and an updated model for asbestos fibers dispersion in ambient environments is proposed.

In situ high-temperature synchrotron powder diffraction study of the thermal decomposition of cement-asbestos

Time-resolved synchrotron powder diffraction was used to follow the thermal transformation of cement-asbestos. Thermal transformation of asbestos fibers into nonfibrous crystalline phases is a promising solution for the elimination of these hazardous minerals. Time resolution offered by the use of an imaging plate detector with a high-brightness X-ray source allowed for the observation of metastable phases, commonly not detectable with conventional instrumentation. In addition, the use of a closed capillary as a sample holder mimicked the real, novel industrial reactor where cement-asbestos slates are sealed in a tunnel kiln. The changing gas atmosphere in the closed system was shown to affect the final composition of the recrystallized product. This study demonstrates the importance of advanced powder diffraction techniques in this field of applied research.

In vitro acellular dissolution of mineral fibres: A comparative study

The study of the mechanisms by which mineral fibres promote adverse effects in both animals and humans is a hot topic of multidisciplinary research with many aspects that still need to be elucidated. Besides length and diameter, a key parameter that determines the toxicity/pathogenicity of a fibre is biopersistence, one component of which is biodurability. In this paper, biodurability of mineral fibres of social and economic importance (chrysotile, amphibole asbestos and fibrous erionite) has been determined for the first time in a systematic comparative way from in vitro acellular dissolution experiments. Dissolution was possible using the Gamble solution as simulated lung fluid (pH = 4 and at body temperature) so to reproduce the macrophage phagolysosome environment. The investigated mineral fibres display very different dissolution rates. For a 0.25 μm thick fibre, the calculated dissolution time of chrysotile is in the range 94–177 days, very short if compared to that of amphibole fibres (49–245 years), and fibrous erionite (181 years). Diffraction and SEM data on the dissolution products evidence that chrysotile rapidly undergoes amorphization with the formation of a nanophasic silica-rich fibrous metastable pseudomorph as first dissolution step whereas amphibole asbestos and fibrous erionite show minor signs of dissolution even after 9–12 months.

Is fibrous ferrierite a potential health hazard? Characterization and comparison with fibrous erionite

Abstract Fibrous erionite is classified by the International Agency for Research on Cancer (IARC) as carcinogenic substance to humans (Group 1). In the areas where it is present in the bedrock, it may cause environmental exposure, and both professional and environmental exposures are possible when the bedrock is used for industrial applications (e.g., building materials). For health and environment protection, prevention is a priority action. In this framework, the recent guidelines of the Consensus Report of the Weinman International Conference on Mesothelioma suggest identifying locations where potentially hazardous mineral fibers (like erionite) are found in the environment, to prevent environmental exposure. The present study will show that one such potentially hazardous mineral fiber might be fibrous ferrierite. Here, the mineralogy, chemical-physical properties, and surface activity of a hydrothermal fibrous ferrierite from Monte Lake British Columbia (Canada) and a diagenetic fibrous ferrierite from Lovelock, Nevada (U.S.A.), were investigated using a combination of “state of the art” experimental methods including optical microscopy, electron microscopy and microprobe analysis, laser ablation-inductively coupled plasma-mass spectrometry (for the trace elements), vibrational spectroscopy, electron paramagnetic resonance, and synchrotron powder diffraction. The chemical-physical properties of these fibrous ferrierites (morphometric parameters, specific surface area, chemical composition with special attention to metals, mainly iron) that prompted adverse effects in vivo were compared to those of the positive carcinogenic standard fibrous erionite-Na from Jersey, Nevada (U.S.A.). The results of our study have demonstrated that, although there are differences in the crystal chemistry and genetic environment, ferrierite samples exhibit outstanding similarities with fibrous erionite samples: both fibrous erionite and fibrous ferrierite may occur in large amounts as microcrystalline fibrous–asbestiform phases in diagenetic rocks with fibers of breathable sizes. For both zeolites, iron is not structural but is associated with impurities lying at the surface of the fibers. Moreover, data useful to understand the surface activity of these fibrous ferrierites were collected. As far as hydrothermal sample is concerned, the EPR data indicate the presence of hydrophilic (SiO-, AlO-, SiOH) and hydrophobic (Si-O-Si) interacting surface groups able to bind the charged CAT1 probes at close sites and attract the probes in the water pools formed into the fiber aggregates. A high percentage of CAT1 probes weakly interacting with the surface due to competition with metal ions were observed for surface of the diagenetic sample. CAT8 probes were less adsorbed by its surface if compared to the diagenetic sample but the more charged surface provided a stronger binding strength for the diagenetic sample compared to the hydrothermal one. In summary, the results of this study indicate that fibrous ferrierite may represent a potential health hazard and, applying the precautionary principle, it should undergo a procedure of toxicity testing.

Synthesis of zeolite LTA films in the presence of nucleation suppressors

The preparation of LTA zeolite films using seeding in combination with film growth in the presence of nucleation suppressors is presented. The films were characterized by X-ray powder diffraction and scanning electron microscopy. It was found that the films had columnar microstructure and that they were preferably oriented with the [111] direction perpendicular (and parallel) to the film surface. The development of preferred orientation was explained by the competitive growth model.