Alessandro Pacella

Combined use of X-ray photoelectron and Mössbauer spectroscopic techniques in the analytical characterization of iron oxidation state in amphibole asbestos

Asbestos fibers are an important cause of serious health problems and respiratory diseases. The presence, structural coordination, and oxidation state of iron at the fiber surface are potentially important for the biological effects of asbestos because iron can catalyze the Haber–Weiss reaction, generating the reactive oxygen species ⋅OH. Literature results indicate that the surface concentration of Fe(III) may play an important role in fiber-related radical formation. Amphibole asbestos were analyzed by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy, with the aim of determining the surface vs. bulk Fe(III)/Fetot ratios. A standard reference asbestos (Union Internationale Contre le Cancer crocidolite from South Africa) and three fibrous tremolite samples (from Italy and USA) were investigated. In addition to the Mössbauer spectroscopy study of bulk Fe(III)/Fetot ratios, much work was dedicated to the interpretation of the XPS Fe2p signal and to the quantification of surface Fe(III)/Fetot ratios. Results confirmed the importance of surface properties because this showed that fiber surfaces are always more oxidized than the bulk and that Fe(III) is present as oxide and oxyhydroxide species. Notably, the highest difference of surface/bulk Fe oxidation was found for San Mango tremolite—the sample that in preliminary cytotoxicity tests (MTT assay) had revealed a cell mortality delayed with respect to the other samples.

New morphological, chemical, and structural data of woolly erionite-Na from Durkee, Oregon, U.S.A.

Abstract A detailed morphological, crystal-chemical, and structural characterization of erionite from the type locality of Durkee, Oregon, has been carried out by combining field emission scanning electron microscopy (FESEM) and laboratory parallel-beam transmission X‑ray powder diffraction (XRPD). According to the crystal-chemical formula (Na5.38K1.99Mg0.24)[Al7.66Si28.34O72.09]·29.83H2O, the sample has been classified as erionite-Na. The Rietveld refinement has indicated that the extraframework cations are located at three Ca1, Ca2, and Ca3 sites, the first one containing all available Mg. Moreover, the absence of the additional K2 site found in both dehydrated erionite and erionite-K has been demonstrated for this erionite sample. Furthermore, our results revealed the absence of Fe and Ca although previous investigations have reported the presence of a variable content of both these elements in erionite samples from Durkee. This is relevant information because it is well known from amphibole asbestos that Fe2+ has been claimed to be one of the causes of carcinogenesis by participating in Fenton chemistry and producing free radicals.

A Deep Look Into Erionite Fibres: an Electron Microscopy Investigation of their Self-Assembly.

The exposure of humans to erionite fibres of appropriate morphology and dimension has been unambiguously linked to the occurrence of Malignant Mesothelioma. For this reason, a detailed morpho-structural investigation through Electron Microscopy techniques has been performed on erionite samples collected at two different localities, Durkee (ED) and Rome (ER), Oregon, USA. The sample from Rome has been also investigated after a prolonged leaching with Gamble’s solution (ER4G) in order to evaluate the possible occurrence of morpho-structural modifications induced by this Simulated-Lung-Fluid (SLF). Here we report how the micrometric erionite fibres evolve in irregular ribbon- or rod-like bundles as a function of different nano-structural features. The reasons for the observed morphological variability have been explained by considering the structural defects located at ED surface fibrils (bi-dimensional ribbons) and the presence of nontronite, an iron-bearing clay mineral embedding the ER fibrils (mono-dimensional rods). ER4G shows a decrease in width of the rod-like fibres due to their partial digestion by SLF leaching, which synchronously dissolves nontronite. The reported results represent a valuable background toward the full comprehension of the morphological mechanisms responsible for potentially damage of lung tissue through the potential relocation of fibers to extrapulmonary sites, increasing the carcinogenic risk to humans.

Iron topochemistry and surface reactivity of amphibole asbestos: relations with in vitro toxicity

Chemical reactivity of asbestos tremolite from Italy and USA localities and Union Internationale Contre le Cancer (UICC) crocidolite was studied in relation to Fe content, oxidation state, and structural coordination. Direct correlation between amount of Fe2+ at the exposed M(1) and M(2) sites of the amphibole structure and fiber chemical reactivity was established. The in vitro toxicity of the same samples was investigated on human alveolar A549 cell line. Relationship between crystal-chemical features and cell toxicity is not straightforward. UICC crocidolite has Fe content and chemical reactivity largely higher than that of tremolite samples, but all show comparable in vitro toxic potential. Results obtained evidenced that Fe topochemistry is not a primary factor for induced cell toxicity, though it accounts for asbestos chemical reactivity (and possibly genotoxicity).

Structural and spectroscopic characterization of a suite of fibrous amphiboles with high environmental and health relevance from Biancavilla (Sicily, Italy)

Abstract This study reports new spectroscopic and structural data of fibrous amphiboles from the volcanic area of Biancavilla (Sicily, Italy) that generated interest because of an anomalous increase of pleural mesothelioma of inhabitants. Each of the four samples is made of loose fibers, which show an edenite-winchite (fluorine) compositional trend, with significant tremolite component. Small amounts of iron (3.6-6.0 wt% FeOtot) were identified in all samples, and the Fe3+/Fetot ratios were evaluated by Mössbauer spectroscopy: two samples are characterized by Fe3+/Fetot ratios between 50 and 70%, and the other two have Fe3+/Fetot ratios higher than 90%. The OH-stretching region was investigated by FTIR, and no absorption bands were observed. Structural investigation was carried out by X-ray powder diffraction using the Rietveld method. Cell parameters, positional parameters for all the atoms, and site scattering for M1, M2, M3, M4, A, and A(m) were refined. The most important differences with respect to prismatic fluoro-edenite are the decrease of β, a, and c with decreasing Ca content, A-site occupancy, and tetrahedral Al content, respectively. By combining chemical, spectroscopic, and structural data, possible site occupancies were obtained. In particular, it was found that Fe2+ is distributed between M1 and M2 sites; moreover, for the two samples enriched in Fe2+, it is also present at M4. Fe3+ is generally ordered at M2 site; however, for the two samples enriched in Fe3+, minor amounts are partially disordered between M1 and M3 sites. For the Biancavilla amphibole fibers, the large compositional variation observed in every sample makes the classification very difficult, so that the regulatory agencies would not classify as “asbestos” the whole mineral series, because of the large components of edenite and winchite in addition to tremolite. Many common features were found with respect to amphibole fibers from Libby, Montana, including Fe contents and oxidation state. Preliminary results of in vitro toxicological tests on Biancavilla fibers confirmed their high reactivity, and suggest that the samples with the highest Fe2+ contents induce a rapid start to cell mortality.

Erionite-Na upon heating: dehydration dynamics and exchangeable cations mobility

Erionite is a fibrous zeolite significantly more tumorigenic than crocidolite asbestos upon inhalation. In recent years, several papers have been published aimed at characterizing from the crystal-chemical point of view erionite fibres. As their toxicity has been ascribed to Fe acquired within the human body, studies aimed at characterizing the iron topochemistry have also been published, suggesting a possible important role played by the ionic exchange properties and cations mobility of this zeolite on developing carcinogenicity. Here we report the analysis results of the thermal behaviour of erionite-Na, which has been found to deviate significantly from that of erionite-K. This result is in contrast with the current scientific view that differences in weighted ionic potential, Si/Al ratio and size of exchangeable cations result in significantly different thermal behaviours, all those parameters being nearly identical or very similar in both species. The different mobility of the extraframework cations observed in erionite samples with dissimilar chemistry is of particular interest within the frame of the hypothesis that their biological activity could depend, apart from surface interactions, also on bulk effects.

Geological occurrence, mineralogical characterization, and risk assessment of potentially carcinogenic erionite in Italy

ABSTRACT Erionite is a zeolite representing a well-known health hazard. In fact, exposure of humans to its fibers has been unequivocally associated with occurrence of malignant mesothelioma. For this reason, a multi-methodological approach, based upon field investigation, morphological characterization, scanning electron microscopy (SEM)/energy-dispersive spectroscopy (EDS) chemical analysis, and structure refinement through X-ray powder diffraction (XRPD), was applied to different samples of potentially carcinogenic erionite from Northern Italy. The studied crystals have a chemical composition ranging from erionite-Ca to erionite-Na and display variable morphologies, varying from prismatic, through acicular and fibrous, to extremely fibrous asbestiform habits. The fibrous samples were characterized by an unusual preferred partition of aluminum (Al) at tetrahedral site T1 instead of tetrahedral site T2. Further, a mismatch between the a-parameter of erionite-Ca and levyne-Ca that are intergrown in the asbestiform sample was detected. This misfit was coupled to a relevant micro-strain to maintain structure coherency at the boundary. Erionite occurs in 65% of the investigated sites, with an estimated quantity of 10 to 40 vol% of the associated minerals. The presence of this mineral is of concern for risk to human health, especially if one considers the vast number of quarries and mining-related activities that are operating in the zeolite host rocks. The discovery of fibrous and asbestiform erionite in Northern Italy suggests the need for a detailed risk assessment in all Italian areas showing the same potential hazard, with specific studies such as a quantification of the potentially respirable airborne fibers and targeted epidemiological surveillance.

Quantitative chemistry and compositional variability offluorine fibrous amphiboles from Biancavilla (Sicily, Italy)

— Compositional variability of the new fluorine fibrous amphiboles (fluoro-edenite) from the volcanic area of Biancavilla (Sicily, Italy) is reported here for the first time. Quantitative chemical analysis of a suite of four samples was performed by a standardized SEM-EDS microanalysis method, previously developed and tested on different typologies of fibrous amphiboles. The results highlighted compositional differences, especially concerning Si, Ca, Fe, and Na contents, both within the same and among the different samples. Compared to the previously investigated fluoro-edenite prismatic variety, the fluorine fibrous amphiboles showed average values of Si and Fe contents always higher, whereas Ca was significantly lower, which we consider a distinctive character for the fluorine fibrous variety. The Fe/Fetot ratios, evaluated by Mossbauer spectroscopy, reflected different iron oxidation states: Fe3+ was always more prevalent than Fe2+, which was very low for two of the four samples analyzed. Employing the Leake classification, all the analyzed fluorine amphibole fibers showed an edenite-winchite trend, with a non negligible content of tremolite component. Both the fluorine amphibole fibers and the prismatic fluoro-edenite from Biancavilla may be correlated with the same genetic process, but the compositional variability reflect different growth conditions. The large variation observed for Fe/Fetot ratios in the amphibole fibers is probably due to local variations of oxygen fugacity during crystallization. A workable hypothesis is that a hot metasomatizing fluid, enriched in fluorine and other incompatible elements, altered the volcanic rocks and caused the crystallization of either the fibrous fluorine amphiboles, by a very fast cooling, or the prismatic fluoro-edenite, by slow cooling. riAssunto. — Viene riportata la variabilita composizionale di alcuni campioni di anfiboli fibrosi (fluoro-edenite) di Biancavilla (Sicilia, Italia), analizzati per la prima volta in modo quantitativo tramite microanalisi SEM-EDS standardizzata, un metodo sviluppato e testato in precedenza dagli stessi autori su diverse tipologie di anfiboli fibrosi. I risultati hanno evidenziato differenze composizionali relative, in particolare, ai contenuti di Si, Ca, Fe e Na, sia all’interno dello stesso campione che tra i diversi campioni analizzati. Un carattere composizionale distintivo tra questi anfiboli fibrosi e la fluoro-edenite prismatica precedentemente studiata e il contenuto sempre piu basso di Ca e sempre piu alto di Si e Fe nella varieta fibrosa. Inoltre i rapporti Fe/Fetot ottenuti sui campioni di fibre tramite spettroscopia Mossbauer hanno evidenziato differenti stati di ossidazione del Quantitative chemistry and compositional variability of fluorine fibrous amphiboles from Biancavilla (Sicily, Italy) simonA mAzziotti-tAgliAni 1, giovAnni b. Andreozzi 1, 2, biAgio m. bruni 3, Antonio giAnfAgnA 1 *, AlessAndro PAcellA 1 and luigi PAoletti 3 1 Dipartimento di Scienze della Terra, Universita degli Studi di Roma La Sapienza, P.le A. Moro, 5, 00185 Roma, Italy 2 Istituto di Geoscienze e Georisorse, CNR, Via G. Moruzzi, 1, 56124 Pisa, Italy 3 Dipartimento di Tecnologie e Salute, Istituto Superiore di Sanita, V.le Regina Elena, 299 , 00162 Roma, Italy Submitted, December 2008 Accepted, March 2009 * Corresponding author, E-mail: antonio.gianfagna@ uniroma1.it 66 s. mAzziotti-tAgliAni, g.b. Andreozzi, b.m. bruni, A. giAnfAgnA, A. PAcellA and l. PAoletti ferro, con il Fe3+ sempre prevalente sul Fe2+ . Secondo la classificazione di Leake, le fibre di anfibolo analizzate mostrano un andamento composizionale edenite-winchite, con un contenuto di tremolite non trascurabile. La variabilita composizionale riscontrata indica pertanto condizioni di crescita differenti, sebbene il processo genetico che ha portato alla formazione delle fibre potrebbe essere lo stesso processo che ha permesso la cristallizzazione della fluoro-edenite prismatica. L’ampia variazione del rapporto Fe/Fetot riscontrata nelle fibre di anfibolo sembrerebbe associata a variazioni locali della fugacita di ossigeno durante la loro cristallizzazione. Sulla base delle indicazioni acquisite e ipotizzabile che un fluido caldo, ricco in F ed altri elementi incompatibili, abbia metasomatizzato le rocce vulcaniche preesistenti e facilitato la cristallizzazione di anfiboli fibrosi (raffreddamento veloce) e di fluoroedenite prismatica (raffreddamento lento).

Surface reactivity of amphibole asbestos: a comparison between crocidolite and tremolite

Among asbestos minerals, fibrous riebeckite (crocidolite) and tremolite share the amphibole structure but largely differ in terms of their iron content and oxidation state. In asbestos toxicology, iron-generated free radicals are largely held as one of the causes of asbestos malignant effect. With the aim of clarifying i) the relationship between Fe occurrence and asbestos surface reactivity, and ii) how free-radical generation is modulated by surface modifications of the minerals, UICC crocidolite and fibrous tremolite from Maryland were leached from 1 day to 1 month in an oxidative medium buffered at pH 7.4 to induce redox alterations and surface rearrangements that may occur in body fluids. Structural and chemical modifications and free radical generation were monitored by HR-TEM/EDS and spin trapping/EPR spectroscopy, respectively. Free radical yield resulted to be dependent on few specific Fe2+ and Fe3+ surface sites rather than total Fe content. The evolution of reactivity with time highlighted that low-coordinated Fe ions primarily contribute to the overall reactivity of the fibre. Current findings contribute to explain the causes of the severe asbestos-induced oxidative stress at molecular level also for iron-poor amphiboles, and demonstrate that asbestos have a sustained surface radical activity even when highly altered by oxidative leaching.

The mechanism of iron binding processes in erionite fibres

Fibrous erionite-Na from Rome (Oregon, USA) was K-exchanged and characterized from the structural point of view. In addition, the modifications experienced after contact with a Fe(II) source were investigated for evaluating if the large potassium ions, blocking off nearly all the erionite cavity openings, might prevent the Fe(II) binding process, which is currently assumed to be one of the reasons of the toxicity of erionite. The K-exchanged sample had a 95% reduction of the BET surface area indicating that it behaves as a mesoporous material. Exchanged K is segregated at K2 and at OW sites commonly occupied by H2O. The latter K cations provide a relevant contribution to the reduction of the surface area. Surprisingly, despite the collapse of its surface area the sample preserves the tendency to bind Fe(II). Therefore, yet in the case of a peculiar and potentially hostile structural environment the Fe(II) ion-exchange process has essentially the same kinetics observed in a typical erionite sample. This is a clear evidence of the very limited effect of the chemical composition of erionite on the Fe(II) binding process and reasonably it does not play a significant role in its toxicity.