Where is iron in erionite? A multidisciplinary study on fibrous erionite-Na from Jersey (Nevada, USA)

Fibrous erionite is a mineral fibre of great concern but to date mechanisms by which it induces cyto- and geno-toxic damage, and especially the role of iron associated to this zeolite species, remain poorly understood. One of the reasons is that we still don\u2019t know exactly where iron is in natural erionite. This work is focused on fibrous erionite-Na from Jersey (Nevada, USA) and attempts to draw a general model of occurrence of iron in erionite and relationship with toxicity mechanisms. It was found that iron is present as 6-fold coordinated Fe3+ not part of the zeolite structure. The heterogeneous nature of the sample was revealed as receptacle of different iron-bearing impurities (amorphous iron-rich nanoparticles, micro-particles of iron oxides/hydroxides, and flakes of nontronite). If iron is not part of the structure, its role should be considered irrelevant for erionite toxicity, and other factors like biopersistence should be invoked. An alternative perspective to the proposed model is that iron rich nano-particles and nontronite dissolve in the intracellular acidic environment, leaving a residue of iron atoms at specific surface sites anchored to the windows of the zeolite channels. These sites may be active later as low nuclearity groups

TG/DSC study of the thermal behaviour of hazardous mineral fibres

This paper reports a systematic and comparative study of the thermal behaviour of fibres of social, health, economic and industrial relevance using thermogravimetric and differential scanning calorimetry (TG/DSC). The mineral fibres selected for the study are: three chrysotile samples, crocidolite, tremolite asbestos, amosite, anthophyllite asbestos and asbestiform erionite. Powder X-ray diffraction and scanning electron microscopy were used for the characterization of the mineral fibres before and after heating at 1000 or 1100 °C to identify the products of the thermal decomposition at a microscopic and structural scale and characterize their thermal behaviour. TG/DSC data allowed the determination of the structural water content and temperature stability. Furthermore, thermal analysis provided a sensitive and reliable technique for the detection of small quantities of different mineral phases occurring as impurities. After thermal treatment, fibrous samples were completely transformed into various iron oxide, cristobalite and other silicate phases which preserved the original overall fibrous morphology (as pseudomorphosis). Only crocidolite at 1100 °C was partially melted, and an amorphous surface was observed

The crystal structure of mineral fibres. 3. Actinolite asbestos

The present work reports chemical and structural data of actinolite asbestos from Aurina Valley, Bolzano (Italy). The chemical composition was determined using EMPA and TG analysis, and the Fe3+/Fetot ratio was accurately evaluated with independent 57Fe M\uf6ssbauer spectroscopy. Morphology and crystallinity were also investigated through SEM and TEM investigations. Crystal structure was refined using high-resolution synchrotron XRPD data. The iron content of Aurina Valley sample is lower compared to two representative asbestiform actinolite samples (with structure refinement) taken from the literature (FeOtot 7.77 wt% against 12\uf713 wt%, respectively), accounting for the reduced cell volume here measured (910.29 \uc5\ub3 against 912\uf7918 \uc5\ub3, respectively). Refined site scattering values of Aurina Valley sample are in agreement with those calculated from chemical compositions, and the optimized structural formula is: K0.02Na0.05(Na0.08Ca1.92)\u1a9=2.00(Mg3.80Fe2+0.79Fe3+0.11Al0.20Mn0.05Ni0.02Cr0.01)\u1a9=4.98(Si7.67Al0.25)\u1a9=7.92O21.69(OH)2.31. The C sites M(1), M(2) and M(3) are occupied by Mg and Fe in a proportion of ~4:1, whereas the M(4) site contains mainly Ca and a very small amount of Na. Iron exclusively occupies the octahedral C sites, with Fe 2+ ions occurring at the M(1,2,3) sites and the small amount of Fe 3+ (13% of Fe tot) ordered at the M(2) site. The refined crystal structure and cation distribution are fully consistent with results previously obtained on asbestiform and non-asbestiform samples belonging to the tremolite-actinolite-ferro\u2013 actinolite substitutional series

Assessment of the potential hazard represented by natural raw materials containing mineral fibres—The case of the feldspar from Orani, Sardinia (Italy)

This work describes the nature of the potentially hazardous fibrous amphibole found in the Orani's feldspar mine (Sardinia, Italy). To identify its nature, a protocol of analysis including morphometric, chemical and crystallographic characterizations was applied. Thanks to this approach, it was possible to classify the observed fibres as tremolite after comparing chemical data, SEM/TEM observations, FTIR/ Raman spectra and X-ray diffraction data with those reported for a standard sample. The unit cell parameters of the investigated tremolite phase are a = 9.82(1) Å, b = 18.08(3) Å, c = 5.27(1) Å, and the angle β corresponds to 104.4(1)°. The mean concentration of asbestos tremolite in the Orani's feldspar is 0.28 wt%. Most of the fibres (0.26 wt%) are respirable ‘regulated’ fibres, representing a potential hazard. Because the total amount of tremolite in the sample is 0.6 wt%, a large fraction of it has a crystal habit other than fibrous-asbestiform or acicular. The obtained results allowed us to suggest possible solutions for a safe exploitation and mineral processing of the Orani's mine. The procedure proposed herein may be a general tool suitable to identify the mineralogical nature of fibrous minerals in raw materials and assess if they may represent a potential health/environmental hazard

Mineral fibres and environmental monitoring: A comparison of different analytical strategies in New Caledonia

Covered by ultrabasic units for more than a third of its surface, the New Caledonia (South West Pacific) is one of the largest world producers of Ni-ore from lateritic deposits. Almost all outcrops of geological units and open mines contain serpentine and amphibole, also as asbestos varieties. In this geological context, in which weathering processes had a great contribution in the production and dispersion of mineral fibres into the environment, the development of a routinely analytical strategy, able to discriminate an asbestiform fibre from a non-harmful particle, is a pivotal requisite. However, the acquisition of all these parameters is necessary for determining the risk associated to fibres exposition. A multidisciplinary routinely approach, based on the use of complementary simply-to-use but reliable analytical methods is the only possible strategy. In addition, the instrumental apparatus must be easily transportable on the field, directly on the mining site. The employment of specialized tools such as Polarized Light Microscopy associated to Dispersion Staining method (PLM/DS) and portable Raman spectroscopy for identification of environmental asbestos, are proved extremely effective in the improvement of the performance and rapidity of data acquisition and interpretation. Both PLM/DS and handheld Raman devices confirmed to be discriminant in the detection and characterization of asbestos fibres for both serpentine and amphibole. Furthermore, these techniques proved extremely effective even in the presence of strongly fibrous and altered samples

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

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