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 asbestosinduced 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

Surface reactivity of amphibole asbestos: A comparison between two tremolite samples with different surface area

Surface reactivity of a fibrous tremolite sample from Castelluccio Superiore (Italy) was investigated by means of free radical generation following incubation in H2O2solution buffered at pH 7.4, for several time points, ranging from 1 day to 1 month. Results obtained were compared with those of another fibrous tremolite sample (from Maryland, USA), with much smaller surface area. Structural, morphological, and chemical alterations induced on tremolite by incubation were investigated by HR-TEM/EDS. The generation of HO•and COO-•radicals following reaction of tremolite with H2O2or formate ion was investigated by spin trapping/EPR spectroscopy. The dissolution process and surface modification were slower for the Maryland sample, with lowest surface area. Surface modification indicated the occurrence of either low- or high-coordinated Fe centres on the surface, as well as the evolution of their nuclearity. In turn, iron centres determine the reactivity of the fibre surface and the yield of HO•and COO-•radical species. The evolution of radical reactivity over time was proved to be largely dependent on surface area, with the highest radical yield occurring for low-area tremolite incubated over long times. The experimental results obtained in this study as well as the comparison with previous studies further confirm that surface reactivity of mineral fibres and inorganic particles is not dependent on Fetotcontent per se, but is likely due to surface properties and occurrence of specific iron sites

HT breakdown of Mn-bearing elbaite from the Anjanabonoina pegmatite, Madagascar

The thermal behavior of a gem-quality purplish-red Mn-bearing elbaite from the Anjanabonoina pegmatite, Madagascar, with composition X(Na0.41□0.35Ca0.24)Σ1.00 Y(Al1.81Li1.00Fe3+ 0.04Mn3+ 0.02Mn2+ 0.12Ti0.004)Σ3.00 ZAl6[T(Si5.60B0.40)Σ6.00O18](BO3)3(OH)3 W[(OH)0.50F0.13O0.37]Σ1.00 was investigated using both in situ High-Temperature X-Ray powder diffraction (HT-pXRD) and ex situ X-Ray single-crystal diffraction (SC-XRD) on two single crystals previously heated in the air up to 750 and 850 °C. The first occurrence of mullite diffraction peaks allowed us to constrain the breakdown temperature of Mnbearing elbaite at ambient pressure, at 825 °C. The breakdown products from the HT-pXRD experiments were cooled down to ambient temperature and identified via pXRD, represented by B-mullite and γ-LiAlSi2O6. A thermally induced oxidation of Mn2+ to Mn3+ was observed with both in-situ and ex-situ techniques; it started at 470 °C and is assumed to be counterbalanced by deprotonation, according to the equation: Mn2+ + (OH)– → Mn3+ + O2– + 1/2H2. At temperatures higher than 752 °C, a partial disorder between the Y and Z sites is observed from unit-cell parameters and mean bond distances, possibly caused by the inter-site exchange mechanism YLi + ZAl → ZLi + YAl

Thermal behavior of schorl up to breakdown temperature at room pressure

Schorl is one of the most widespread tourmaline compositions in the world, known from many different geological settings. Its role as boron and water carrier has been moderately investigated together with its stability field. In this study, the richest schorl in Fe2+ content was investigated to constraint its breakdown temperature at room pressure through in situ powder X-Ray Diffraction (in situ pXRD), its breakdown products and the coupled thermally induced dehydrogenation-dehydrogenation process experienced approaching the breakdown conditions. Schorl turned out to begin its breakdown at 850 °C with the first appearance of hematite, followed by a dominant B-mullite phase. The breakdown reaction of schorl can be expressed as follows: 2NaFe2+3Al6(BO3)3Si6O18(OH)=3Fe2O3+4/3Al9Si2BO19+(Na- Si- B-rich) glass+4H2O.The breakdown process is completed at 950 °C, when no trace of residual tourmaline is found. Annealing the schorl at 450 °C in air was enough to set the Fe oxidation out, counterbalanced by the deprotonation reaction: (Fe2+)+(OH)- → (Fe3+)+ (O2-)+1/2H2(g)

Diamond-inclusion system recording old deep lithosphere conditions at Udachnaya (Siberia)

Diamonds and their inclusions are unique fragments of deep Earth, which provide rare samples from inaccessible portions of our planet. Inclusion-free diamonds cannot provide information on depth of formation, which could be crucial to understand how the carbon cycle operated in the past. Inclusions in diamonds, which remain uncorrupted over geological times, may instead provide direct records of deep Earth’s evolution. Here, we applied elastic geothermobarometry to a diamond-magnesiochromite (mchr) host-inclusion pair from the Udachnaya kimberlite (Siberia, Russia), one of the most important sources of natural diamonds. By combining X-ray diffraction and Fourier-transform infrared spectroscopy data with a new elastic model, we obtained entrapment conditions, Ptrap = 6.5(2) GPa and Ttrap = 1125(32)–1140(33) °C, for the mchr inclusion. These conditions fall on a ca. 35 mW/m2 geotherm and are colder than the great majority of mantle xenoliths from similar depth in the same kimberlite. Our results indicate that cold cratonic conditions persisted for billions of years to at least 200 km in the local lithosphere. The composition of the mchr also indicates that at this depth the lithosphere was, at least locally, ultra-depleted at the time of diamond formation, as opposed to the melt-metasomatized, enriched composition of most xenoliths

Bulk spectroscopy of mineral fibres

Spectroscopic methods are utilized widely for characterizing minerals and other geomaterials in terms of electronic, vibrational and nuclear properties. The basics and applications of spectroscopic methods in mineralogy were reported comprehensively by Hawthorne (1988), and later discussed carefully and updated by Burns (1993) and Clark (1999), by Beran and Libowitzky (2004) and more recently by Henderson et al. (2014). These esteemed books and reviews focused generally on topics of immediate mineralogical interest, but nevertheless contain stimulating parallel excursions into the fields of geology and materials sciences. This chapter is built on the shoulders of those giants and is devoted specifically to exploring spectroscopic investigations of electronic and nuclear properties of mineral fibres, a topic not reviewed previously. A number of spectroscopies (though not all) will be mentioned without covering in detail their physical bases (which can be found easily in the books and reviews mentioned above), because this chapter is intended to serve as a review of their contribution to increasing comprehension of the bulk properties of mineral fibres

Crystal structure and iron topochemistry of erionite-K from Rome, Oregon, U.S.A

aBstract A complete crystal-chemical characterization of erionite-K from Rome, Oregon, was obtained by combining field emission scanning electron microscopy, laboratory parallel-beam transmission powder diffraction, and 57 Fe Mössbauer spectroscopy. Rietveld refinement results evidenced that the most striking difference in comparison with the structure of erionite-Ca is significant K at a K2 site (½, 0, 0), which is empty in erionite-Ca. In addition, site Ca1 shows low occupancy and Ca3 is vacant. The oxidation and coordination state of Fe, whose occurrence was revealed by chemical analysis, have been clarified by exploiting room-and low-temperature 57 Fe Mössbauer spectroscopy. The majority of Fe (95%) was attributed to Fe 3+ -bearing, superparamagnetic, oxide-like nanoparticles with dimensions between 1 and 9 nm, and the remaining 5% was attributed to hematite particles with size ≥10 nm, both located on the crystal surface

Preface: The 8th European conference on mineralogy and spectroscopy

Preface to the special ECMS 2015 Conference held in Rome (Italy

Preface: The 8th European conference on mineralogy and spectroscopy

Preface to the special ECMS 2015 Conference held in Rome (Italy

Fe–Mg substitution in aluminate spinels. Effects on elastic properties investigated by Brillouin scattering

We investigated by a multi-analytical approach (Brillouin scattering, X-ray diffraction and electron microprobe) the dependence of the elastic properties on the chemical composition of six spinels in the series (Mg1−x,Fex)Al2O4(0 ≤ x ≤ 0.5). With the exception of C12, all the elastic moduli (C11, C44, KS0and G) are insensitive to chemical composition for low iron concentration, while they decrease linearly for higher Fe2+content. Only C12shows a continuous linear increase with increasing Fe2+across the whole compositional range under investigation. The high cation disorder showed by the sample with x = 0.202 has little or no influence on the elastic parameters. The range 0.202 < x < 0.388 bounds the percolation threshold (pc) for nearest neighbor interaction of Fe in the cation sublattices of the spinel structure. Below x = 0.202, the iron atoms are diluted in the system and far from each other, and the elastic moduli are nearly constant. Above x = 0.388, Fe atoms form extended interconnected clusters and show a cooperative behavior thus affecting the single-crystal elastic moduli. The elastic anisotropy largely increases with the introduction of Fe2+in substitution of magnesium in spinel. This behavior is different with respect to other spinels containing transition metals such as Mn2+and Co2+