Could soluble minerals be hazardous to human health? Evidence from fibrous epsomite.

From a toxicological point of view, particulates and fibres with high solubility in water and/or in biological environments have not been considered in detail and the knowledge to date in this area is very scarce. In this study, the water-soluble natural epsomite fibres from Perticara Mine (Italy) were investigated using SEM-EDS, XRPD, ICP-AES and alpha spectrometry measurements which were combined and integrated to characterise the fibres' morphology, crystal chemistry and mineralogy. The morphological and morphometric results showed that most of the fibres are of inhalable size (Dae 5.09 µm) and can be potentially adsorbed from all parts of the respiratory tract. Chemical analysis reveals significant amounts of toxic elements (As, Co, Fe, Mn, Ni, Sr, Ti, Zn) and surprisingly high contents of radioactive isotopes (210Po and 228Th) in epsomite crystals, making the inhalation of these fibres potentially hazardous to human health. Through this study, we want to focus on soluble minerals, such as epsomite, which can be present in both natural and anthropic environments and have never been considered from the point of view of their potential hazard.

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

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.

Electron paramagnetic resonance and transmission electron microscopy study of the interactions between asbestiform zeolite fibers and model membranes.

Different asbestiform zeolite fibers of the erionite (termed GF1 and MD8, demonstrated carcinogenic) and offretite (termed BV12, suspected carcinogenic) families were investigated by analyzing the electron paramagnetic resonance (EPR) spectra of selected surfactant spin probes and transmission electron microscopy (TEM) images in the presence of model membranes-cetyltrimethylammonium (CTAB) micelles, egg-lecithin liposomes, and dimyristoylphosphatidylcholine (DMPC) liposomes. This was undertaken to obtain information on interactions occurring at a molecular level between fibers and membranes which correlate with entrance of fibers into the membrane model or location of the fibers at the external or internal membrane interfaces. For CTAB micelles, all fibers were able to enter the micelles, but the hair-like structure and chemical surface characteristics of GF1 modified the micelle structure toward a bilayer-like organization, while MD8 and BV12, being shorter fibers and with a high density of surface interacting groups, partially destroyed the micelles. For liposomes, GF1 fibers partially penetrated the core solution, but DMPC liposomes showed increasing rigidity and organization of the bilayer. Conversely, for MD8 and BV12, the fibers did not cross the membrane demonstrating a smaller membrane structure perturbation. Scolecite fibers (termed SC1), used for comparison, presented poor interactions with the model membranes. The carcinogenicity of the zeolites, as postulated in the series SC1

Potential carcinogenic erionite from Lessini Mounts, NE Italy: Morphological, mineralogical and chemical characterization.

Exposure of humans to erionite fibers of suitable morphology and dimension has been unambiguously linked to the occurrence of malignant mesothelioma. For this reason, a morphological, morphometrical, mineralogical, and chemical investigation was performed on two representative samples of potential carcinogenic, fibrous erionite from Lessini Mounts, northeastern (NE) Italy, which has not apparently been examined previously. The first sample is erionite-Ca with an extremely fibrous, hair-like and flexible appearance, and growth in intimate association with levyne. The second sample is erionite-Ca with prismatic to acicular crystals and rigid behavior, enriched in K(+) and Ca(2+) extra-framework cations. Although erionite is a nominally Fe-free phase, iron (Fe) was detected in low amounts in all the analyzed crystals. In both the investigated samples, erionite is present as individual fibers of respirable size. Considering that the toxicity and carcinogenic potential of erionite is associated with its size parameters, together with its in vivo durability and high surface area, most of the investigated fibers may also be potentially carcinogenic. The presence of erionite in extensively quarried and largely employed volcanic rocks, suggesting the need for detailed health-based studies in the region.

Essential and toxic elements in clays for pharmaceutical and cosmetic use.

Essential and toxic elements (Al, Si, P, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Ba, Cd, Ce, Nd, Pb, U, Th, and La) were determined by energy-dispersive polarized x-ray fluorescence spectrometry (EDPXRF) in 15 samples of clay materials for pharmaceutical and cosmetic use. The investigated samples were grouped according to their mineralogical composition determined by x-ray powder diffraction (XRPD). Samples consisting of smectites showed the lowest content of K, Zn, La, Ce, Nd, Pb, Ti, and Th and highest quantity of Sr, Br, and U. The sample containing smectite and kaolinite displayed the lowest content of Ca, Fe, Mn, Cu, Ni, and Sr and highest amount of Al, Si, Ba, Zn, As, La, Ce, Pb, and Th. Samples composed of illite demonstrated minimal amounts of Br and maximal content of K, Rb, Ti, and Fe. In all samples analyzed, Cd and Hg levels were below 2 mg/kg.

The in vitro cytotoxic effects of natural (fibrous epsomite crystals) and synthetic (Epsom salt) magnesium sulfate.

Exposure to mineral fibers represents an occupational and environmental hazard since particulate inhalation leads to several health disorders. However, few data are available on the effect of fibers with high solubility like natural epsomite, a water-soluble fiber with an inhalable size that allows it to penetrate biological systems, with regard to the respiratory tract. This study evaluated the natural (fibrous epsomite) and synthetic (Epsom salt) magnesium sulfate pathogenicity. Investigations have been performed through morpho-functional and biochemical analyses, in an in vitro cell model that usually grows as monocytes, but that under appropriate conditions differentiates into macrophages. These latter, known as alveolar macrophages, if referred to lungs, represent the first line of defense against harmful inhaled stimuli. Morphological observations reveal that, if Epsom salt induces osmotic stress on cell culture, natural epsomite fibers lead to cellular alterations including thickening of the nuclear envelope and degenerated mitochondria. Moreover, the insoluble fraction (impurities) internalized by cells induces diffuse damage characterized at the highest dosage and exposure time by secondary necrosis or necrotic cell death features. Biochemical analyses confirm this mineral behavior that involves MAPK pathway activation, resulting in many different cellular responses ranging from proliferation control to cell death. Epsom salt leads to MAPK/ERK activation, a marker predictive of overall survival. Unlike, natural epsomite induces upregulation of MAPK/p38 protein involved in the phosphorylation of downstream targets driving necrotic cell death. These findings demonstrate natural epsomite toxicity on U937 cell culture, making the inhalation of these fibers potentially hazardous for human health. RESEARCH HIGHLIGHTS: Natural epsomite and synthetic Epsom salt effects have been evaluated in U937 cell model. Epsom salt induces an osmotic cellular stress. Natural epsomite fibers lead to cellular damage and can be considered potentially dangerous for human health.

The crystal structure of the killer fibre erionite from Tuzköy (Cappadocia, Turkey).

Erionite is a non-asbestos fibrous zeolite classified by the International Agency for Research on Cancer (IARC) as a Group 1 carcinogen and is considered today similar to or even more carcinogenic than the six regulated asbestos minerals. Exposure to fibrous erionite has been unequivocally linked to cases of malignant mesothelioma (MM) and this killer fibre is assumed to be directly responsible for more than 50% of all deaths in the population of the villages of Karain and Tuzköy in central Anatolia (Turkey). Erionite usually occurs in bundles of thin fibres and very rarely as single acicular or needle-like fibres. For this reason, a crystal structure of this fibre has not been attempted to date although an accurate characterization of its crystal structure is of paramount importance for our understanding of the toxicity and carcinogenicity. In this work, we report on a combined approach of microscopic (SEM, TEM, electron diffraction), spectroscopic (micro-Raman) and chemical techniques with synchrotron nano-single-crystal diffraction that allowed us to obtain the first reliable ab initio crystal structure of this killer zeolite. The refined structure showed regular T-O distances (in the range 1.61-1.65 Å) and extra-framework content in line with the chemical formula (K2.63Ca1.57Mg0.76Na0.13Ba0.01)[Si28.62Al7.35]O72·28.3H2O. The synchrotron nano-diffraction data combined with three-dimensional electron diffraction (3DED) allowed us to unequivocally rule out the presence of offretite. These results are of paramount importance for understanding the mechanisms by which erionite induces toxic damage and for confirming the physical similarities with asbestos fibres.

Characterisation of potentially toxic natural fibrous zeolites by means of electron paramagnetic resonance spectroscopy and morphological-mineralogical studies.

This study explored the morphological, mineralogical, and physico-chemical features of carcinogenic erionite and other possibly hazardous zeolites, such as mesolite and thomsonite, while also investigating the interacting capability of the mineral surface at the liquid/solid interface. Extremely fibrous erionite is K+ and Ca2+-rich and shows the highest Si/Al ratio (3.38) and specific surface area (8.14 m2/g). Fibrous mesolite is Na+ and Ca2+-rich and displays both a lower Si/Al ratio (1.56) and a smaller specific surface area (1.56 m2/g). The thomsonite composition shows the lowest values of Si/Al ratio (1.23) and specific surface area (0.38 m2/g). Electron paramagnetic resonance data from selected spin probes reveal that erionite has a homogeneous site distribution and interacts well with all spin probes. The surfaces of mesolite and thomsonite are less homogeneous and closer polar sites were found through consequent interaction with the probes. The mesolite surface can also clearly interact but with a lower strength and may represent a potential health hazard for humans, though with a lower degree if compared to erionite. The thomsonite surface is not inert and interacts with the probes with a low-grade capability. We can expect small fragments of thomsonite to interact with the biological environment, though with a low-grade intensity.

Mineralogical dataset of natural zeolites from Lessini Mounts, Northern Italy: Analcime, natrolite, phillipsite and harmotome chemical composition.

This dataset article contains mineralogical and chemical data of some natural zeolites such as analcime, natrolite, phillipsite and harmotome. These minerals were found as secondary phases within vesicles and veins in the basaltic rocks of the Lessini Mounts, Northern Italy. Methods for obtaining the datasets include optical microscopy, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Analcime forms well-developed, transparent to milky crystals with a typical icositetrahedron habit. The average composition of analcime is calculated as Na13.79Ca0.01K0.03Ba0.03[Al14.28Si33.82O96] 16H2O, with all of the extra-framework sites occupied by sodium. Natrolite usually forms hemispherical aggregates with glassy, colourless to white thin prismatic crystals, which generally radiate from a central point. The average chemical composition of natrolite is Na14.28Ca0.14K0.01[Al15.60Si24.59O80] 16H2O. Crystals of phillipsite-harmotome serie occur in a variety of forms and display a highly variable chemical composition, from almost pure compositions to intermediate values. Phillipsite is more common and its average chemical composition is Ca1.40Na0.29K1.08Ba0.27[Al4.68Si11.28O32] 12H2O, while harmotome is rare and has an average chemical composition of Ca0.97Na0.20K0.36Ba0.91[Al4.60Si11.46O32] 12H2O. The obtained dataset can be used for various purposes: it can be used by other authors to compare morphological features and chemical compositions of similar zeolites crystals discovered in other parts of the world, it can be compared with those obtained from similar geologic environments encouraging studies on hydrothermal processes, and it could represent the starting point for a potential exploration of zeolites from an industrial point of view.

Petrographic and mineral-glass chemical dataset of igneous rock clasts from Early Oligocene Aveto-Petrignacola Formation (Northern Italy).

This dataset article contains petrographic and mineral-glass chemical data of igneous rock clasts from Early Oligocene Aveto-Petrignacola Formation (APF; Northern Italy). Methods for obtaining the dataset include optical microscopy, scanning electron microscopy and electron probe microanalysis. The APF volcanic rocks are basalts, basaltic andesites, andesites, dacites and rhyolites. Rare gabbroic cumulate nodules complete the dataset. Basalts are porphyritic, with calcic plagioclase (An72-92Ab7-27Or0-1), ferroan enstatite (En59-68Fs29-37Wo3-4) and augite (En38-39Fs18-20Wo41-44) phenocrysts, in a hypocrystalline groundmass made up of bytownite (An71-85Ab14-28Or1), augite (En37-38Fs19Wo43-44), ferroan enstatite (En62-68Fs30-35Wo1-4) and rare pigeonite (En46-50Fs37-42Wo7-17). The basaltic andesites are porphyritic to glomeroporphyritic with phenocrysts of zoned plagioclase (An44-67Ab32-55Or1), orthopyroxene, Mg-rich augite (En38-42Fs15-17Wo43-45), rare pargasite to edenite amphibole (Mg# 69-59) and very rare biotite in a hypocrystalline to holohyaline groundmass. Andesites are highly porphyritic with phenocrysts of plagioclase (An47-79Ab20-52Or0-1), pargasite to magnesio-hornblende (Mg# 72-67), Mg-rich augite (En43-46Fs12-17Wo41-43), subordinate ferroan enstatite (En68-74Fs23-29Wo3-4), biotite (Mg# 53) and Ti-magnetite (Usp29-41). Dacites (massive lavas and ignimbrites) are porphyritic, with phenocrysts and phenoclasts of plagioclase (An33-79Ab20-62Or0-4), calcic amphibole (Ti-pargasite, Mg-hornblende and edenite; Mg# 81-46), biotite (Mg# 67-56), very rare Mg-rich augite (En41-42Fs16-18Wo40-43) and resorbed quartz in hypohyaline to holohyaline groundmass with a dense mat of anhedral quartz, labradorite-andesine (An36-66Ab33-61Or1-4) and rare anorthoclase (An22Ab66Or12). Rhyolitic compositions have been found both as volcanic clasts (massive lava and ignimbrites) with andesine to oligoclase phenoclasts (An25-38Ab61-71Or1-4), quartz, biotite (Mg# 55-53) and Ti-magnetite (Usp18-77), and as interstitial glasses (residual melt drops) in other APF volcanic rocks. The cumulate nodules are olivine-gabbro and amphibole-gabbro/gabbronorite with a mineral paragenesis dominated by plagioclase (An41-73Ab26-57Or1-3), olivine (Fo68-72), Mg-rich augite to ferroan diopside (En41-45Fs12-15Wo42-45; Mg# 79-74), ferroan enstatite (En65-74Fs24-33Wo2-3; Mg# 76-68), magnetite (Usp15-28) and titanian pargasite (Mg# 67-65). The main cumulus phases are plagioclase, olivine and pyroxene, while intercumulus/postcumulus phases are titanian pargasite and magnetite. The dataset can be used to compare petrographic features and chemical compositions of calc-alkaline rocks emplaced in other subduction-related settings. Above all, it can represent a useful contribution in solving the problem linked to the identification of a hidden Early-Oligocene source of the thick volcaniclastic APF succession in the Alpine-Apennine belt geodynamic evolution.

In vitro effects on calcium oxalate crystallization kinetics and crystal morphology of an aqueous extract from Ceterach officinarum: Analysis of a potential antilithiatic mechanism.

Ceterach officinarum Willd is a plant widespread throughout Europe and used in southern Italy as a diuretic. Beliefs in the benefits of C. officinarum aqueous extract in the treatment of calcium oxalate kidney stones are widely held. Little is known, however, about the actual mechanism of its antilithiatic action. Our results in this in vitro study corroborate C. officinarum aqueous extract as a good source of antioxidants with a high antioxidant effects. Our results also demonstrate a major impact of C. officinarum aqueous extract on in vitro induced calcium oxalate crystallization kinetics and crystal morphology, showing its critical role in kidney stone formation and/or elimination. We show that progressively increasing doses of C. officinarum aqueous extract cause a sequence of effects. A powerful inhibitory action on calcium oxalate monohydrate (COM) growth and aggregation is first observed. C. officinarum aqueous extract also appears highly effective in stimulating nucleation increasing the number and reducing the size of COM crystals, which become progressively thinner, rounded and concave in a dose-dependent manner. These shape-modified COM crystals are known to be less adherent to renal tubular cells and more easily excreted through the urinary tract preventing kidney stone formation. Further, C. officinarum aqueous extract promotes the formation of calcium oxalate dihydrate (COD) rather than the monohydrate so that, at the highest concentrations used, only COD crystals are observed, in significant greater numbers with a clear reduction in their size, in a dose-dependent manner. Furthermore, AFM analyses allowed us to reveal the presence of C. officinarum component(s) on the surfaces of COD and modified COM crystals. The crystal surface adsorbed component(s) are shown to be similarly active as the total aqueous extract, suggesting a trigger factor which may direct crystal modification towards COD forms. In urolithiasis pathogenesis COD crystals are less dangerous than the COM forms due to their lower affinity for renal tubular cells. Our results are important in understanding the mechanisms which guide the modification induced by C. officinarum on the crystallization process. Based on these data, together with no adverse toxic effect being observed on the in vitro model of human intestinal enterocytes, C. officinarum aqueous extract could represent an attractive natural therapy for the treatment of urolithiasis.

EPR, TEM and cell viability study of asbestiform zeolite fibers in cell media.

Human monocyte U937 cell line was used as a model to verify the toxicity of erionite and offretite asbestiform zeolite fibers. As a presumed non-toxic reference, a fibrous scolecite zeolite was also used. To analyze the process of fiber ingestion into cells and the cells-fibers interactions, a spin-probe electron paramagnetic resonance (EPR) analysis was performed supported by transmission electron microscopy (TEM) and cell viability measurements as a function of the incubation time. Erionite fibers were fast internalized in the membrane mainly as aggregates with radical-solution drops trapped inside, and were found in the cytosol and at the nucleus. In 24h, first erionite fibers rich in sodium and potassium, and then calcium-rich erionite fibers, induced cell necrosis. The offretite fibers formed rounding electron-dense filaments which transformed in curved filaments, initially perturbing the cell structure and interacting at the external surface more than erionite fibers. Such interactions probably diminished the toxic effect of offretite on cells. Interestingly, the presumed non-toxic scolecite fibers were partially internalized, inducing formation of swollen mitochondria and squared cells. Overall, the toxic effect of the fibrous zeolites was related to fiber morphology, chemical distribution of sites, structural variations and formation of aggregates.

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers.

Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si-O-Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity.