Michele Mattioli

Early activity of the largest Cenozoic shield volcano in the circum-Mediterranean area: Mt. Karacadag, SE Turkey

Volcanic activity at Mt. Karacadag, SE Turkey, developed between ~11 and ~0.01 Ma. In this paper we investigate the oldest products (older than 2.6 Ma) that created a large volcanic plateau and a N-S aligned volcanic edifice in the form of a shield volcano. These igneous rocks are mildly alkaline to transitional olivine-clinopyroxene phyric basalts with minor hawaiites, basanites and very rare differentiated lithologies (mugearites and benmoreites). The poor correlation of major elements with MgO in these lavas is qualitatively consistent with polybaric depths of magma production, variable degrees of partial melting (from ~2 to ~10 %), heterogeneous mantle sources and differences in the fractionating crystal assemblage. Primitive mantle-normalized patterns resemble typical anorogenic magma compositions, with peaks at HFSE (Nb, Ta, Hf, Zr) and high HFSE/LILE ratios. REE contents are compatible with derivation of the basanites from a mixed garnet-spinel facies peridotite after ~2 % partial melting. Alkali basalts are compatible with higher degrees of melting (between 5 and 10 %) from the same type of source. Initial 87 Sr/ 86 Sr ratios range from 0.70349 to 0.70522 while those of 143 Nd/ 144 Nd range from 0.512853 to 0.512659. Early-stage lavas show higher 87 Sr/ 86 Sr and lower 143 Nd/ 144 Nd compared to plateau-stage lavas. The Sr-Nd isotopic variations and their relation with major and trace elements cannot be explained by AFC-like (Assimilation and Fractional Crystallization) processes involving average crustal lithologies. More likely, the Sr-Nd isotopic ratios are related to the existence of heterogeneous mantle sources with only minor involvement of AFC-like processes. The Cenozoic lavas in a 200 x 800 km area between the Karasu Valley and the Syria-Iraq-Turkey border in south-eastern Anatolia form a distinct igneous province which can be characterised on the basis of Sr-isotope signatures. The lithospheric mantle beneath this area is characterized by anomalously enriched 87 Sr/ 86 Sr compositions (up to 0.7055) as well as more isotopically depleted compositi o ns ( 87 Sr/ 86 Sr down to 0.7030).

High-Mg Tertiary basalts in Southern Sardinia (Italy)

Abstract High-Mg basaltic pillow lavas, important for an understanding of the petrogenetic evolution of the Tertiary volcanism of Sardinia, have recently been recognized in the lower part of the Early-Burdigalian volcano-sedimentary succession of the Villanovaforru (VF) area (Southern Sardinian Trough). Their textures vary from porphyritic to highly phyric types (doleritic) and the paragenesis is represented by Pl+Ol+Cpx±Opx±Opq. These basalts are sub-alkaline with a tholeiitic tendency; they display high MgO (mg-number 64–68), high Ni and Cr contents and their geochemical features are related to subduction-related magmas, with large-ion lithophile element enrichment and negative Nb, Zr and Ce spikes in mantle-normalized diagrams. The mineralogical and geochemical characteristics indicate that the VF basalts crystallized from primitive magmas within an extension-dominated tectonic setting. The presence of primitive basalts suggests crustal thinning in association with the Burdigalian extensional tectonics affecting the Sardinian Trough.

Silicate melt inclusions in the cumulate minerals of gabbroic nodules from Stromboli Volcano (Aeolian Islands, Italy): main components of the fluid phase and crystallization temperatures

Abstract The studied gabbroic nodules occurring in the Petrazza pyroclastic rocks consist mainly of plagioclase (An95-87), olivine (Fo83-73) and clinopyroxene (Mg# 90-77), with subordinate opaques (Ti-magnetite) and amphibole (Mg-hastingsite), which constitute the cumulate minerals. Interstitial material has a relatively high, but variable, degree of vesicularity and consists of variable amounts of glass and quenched crystals of plagioclase (An71-55), amphibole, clinopyroxene and rare biotite, olivine and opaques. Silicate melt inclusions are abundant in the cumulate minerals, but complete homogenization to melt has been observed only in the inclusions occurring in clinopyroxene, where the temperatures of homogenization vary from 1134 to 1190ºC. Microthermometric investigations of fluid inclusions and of the shrinkage bubble of the melt inclusions suggest that the magma contained CO2. The apparent scarcity of H2O indicates that this component was strongly partitioned into the magma at the time of crystallization of the investigated minerals; this is further supported by the occurrence of (1) daughter biotite- and amphibole-bearing inclusions which show that the H2O activity in the magma was sufficiently high to allow their crystallization, and (2) calcic plagioclase (An95-87) which can be crystallized from a high-alumina basaltic magma at pressure 42 kbar, temperatures in the range 1050-1100ºC and in the presence of 3-4 wt.% of water (MELTS software simulations). The composition of the melt inclusions suggests that the hosting plagioclase, olivine and clinopyroxene crystallized from slightly different batches of magma. The S content in the melt inclusions of clinopyroxene and olivine is high (up to 0.41 wt.%). The presence of Fe-Cu(-Ni)-rich blebs of sulphide in plagioclase, olivine, amphibole, and locally in the melt inclusions too, further supports the important role of sulphur in the primitive magmas of the investigated gabbros. Small differences in redox conditions or in the Fe content of the melts favoured S mobilization as sulphide.

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.

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.

Secondary mineral assemblage as indicator of multistage alteration processes in basaltic lava flows: evidence from the Lessini Mountains, Veneto Volcanic Province, Northern Italy

The secondary mineral assemblages in the Tertiary basalts from the Lessini Mountains are mainly clay minerals and zeolites, and result from multistage alteration processes. In the earliest Stage I, clay and silica minerals precipitate along the inner walls of the vesicles, followed by the deposition of the fine-grained zeolites of the Stage II (erionite, offretite, analcime, natrolite, heulandite and stilbite). The final Stage III is marked by a new generation of large, well-shaped zeolites (phillipstite-harmotomo, gmelinite, chabazite, willhendersonite and yugawaralite), followed by extensive crystallization of calcite. New morphological and chemical data are presented herein in order to reveal the chemical compositions of Lessini zeolite species, which have never been analyzed before. Textural and chemical observations indicate that the chemical elements for Stage I and II alteration minerals derived from the alteration of the basaltic glass and the primary phases in the volcanic host rocks. The final mineral assemblages of the Stage III suggest a variation in the crystallization conditions, probably related to the presence of new, late-stage fluids enriched in Ca and (CO 3 ) 2- , leached from the surrounding calcareous rocks.

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.

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

ABSTRACT 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 Ca2+ 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.

Raman and micro-thermometric investigation of the fluid inclusions in quartz in a gold-rich formation from Lepaguare mining district (Honduras, Central America)

Fluid inclusions in the quartz crystals present in gold-rich veins from central Honduras have been studied by means of micro-thermometry and micro-Raman spectroscopy in order to provide information on the physico-chemical conditions and chemical composition of the mineralizing fluids. The use of a confocal micro-Raman apparatus allowed to obtain information on the fluid composition, in particular on the gas phase, minimizing the contributions of the host matrix to the Raman signal. The samples studied were collected from an area (Lepaguare mining district, Northern-Central Honduras) rich in ore deposits due to the Cenozoic magmatic activity, where the gold and sulphide mineralization is connected with a system of quartz veins (few decimetres thick) occurring in low-grade metamorphic rocks and produced by hydrothermal fluids. The quartz crystals present in the gold-rich veins often contain fluid inclusions. Four types of fluid inclusions have been observed, but their assemblage in the same clusters and fracture systems, as well as their comparable salinity and homogenization data, suggest that they have the same origin. Micro-thermometry and Raman spectroscopy provide a composition of the mineralizing fluids attributable to the system H(2)O-NaCl-KCl-CO(2)-CH(4), with temperature and pressure intervals of 210-413 degrees C and 1050-3850 bar, respectively. These data agree with an epigenetic origin of the gold deposit (depth < 6 km) related to granitoid or granodiorite intrusions associated to orogenic environments.

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

ABSTRACT 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