Paolo Mazzoleni

Clay Mineral Assemblages and Sandstone Compositions of the Mesozoic Longobucco Group, Northeastern Calabria: Implications for Burial History and Diagenetic Evolution

Mesozoic mudrocks and sandstones from the Longobucco Group (Sila Unit, North Calabria) were mineralogically, chemically, and petrographically analyzed for their burial, diagenesis, and sourcearea weathering histories. These sediments mark an important phase of the regional geological evolution along internal domains of the circum-Mediterranean chains from the Gibraltar Arc (Spain and Morocco) to the Calabria-Peloritani orogen (Italy). The effects of diagenesis on quartzose sandstone-mudstone lithotypes in the Mesozoic Longobucco Group succession are quantified. The basal Longobucco Group consists of continental clastic redbeds deposited in a rapidly subsiding rift-valley basin, overlain by shallow-marine to deep-marine carbonate and clastic strata. These sediments were analyzed using thin-section petrography, SEM/EDS, X-ray diffraction (XRD), and fluorescence. Quartzarenites display heterogeneous distributions of authigenic quartz, kaolin, illite, feldspar, and minor carbonate cementation. Authigenic zoned syntaxial overgrowths on detrital quartz represent the principal cement, and interstitial clay is an important component of these lithotypes. The mineralogical assemblage of mudrocks is dominated by illite and illite/smectite mixed layers. This observation, coupled with the CIA index and the A-CN-K plot, suggests post-depositional K-enrichment. Paleoweathering indices (CIW and PIA ratios) suggest that the source experienced intense weathering and that mudrocks likely record recycling from metasedimentary basement rocks. Clay-mineral distributions of sandstone/mudstone lithotypes indicate that mixed-layer illite/smectite with ordered interstratification (from R = 1 to R = 3) dominates mudstone mineralogy. Authigenic clays in sandstone are kaolinite, illite, chlorite, and kaolinite illitization as pore filling and lining. These authigenic clays show a distinct distribution, reflecting differences in burial/temperature history. The illite crystallinity index, the illitization of kaolinite, and the occurrence of high-illite I/S mixed-layer clay minerals suggest burial depths of at least 4-6 km and a temperature typical of the boundary between late diagenesis to low anchizone.

Mid-Ordovician U–Pb ages of porphyroids in the Peloritan Mountains (NE Sicily): palaeogeographical implications for the evolution of the Alboran microplate

Petrographic, geochemical and geochronological work on a metavolcanic suite interbedded in a metapelitic sequence of the Palaeozoic basement in the Peloritan Mountains (Sicily) is used to contribute to a better understanding of the pre-Variscan geodynamic evolution of the former Alboran microplate. Major and trace element data show that the volcanic suite consists of two main groups: an Intermediate Unit of andesites and dacites with volcanic arc affinity and a Felsic Porphyroid Unit of rhyolites with peraluminous composition. Isotope dilution thermal ionization mass spectrometry U–Pb analyses for single- and multigrain zircon fractions from four samples of the felsic porphyroids yield results that are tightly clustered on or near concordia giving Caradoc ages in the range of 456–452 Ma. The consistent morphological characteristics and oscillatory zoning of the zircons indicate single-stage magmatic crystallization. Xenocrystic zircon grains with ages of 1150 and 2015 Ma indicate that these rocks were developed upon a cratonic basement with Grenvillian and Transamazonian components, hence supporting a peri-Gondwanan origin. From the combined evidence we conclude that this portion of the Alboran microplate formed as a Mid-Ordovician volcanic arc in a sector of the peri-Gondwanan terranes that was affected by a tectonothermal Caradoc event.

Combined non-destructive XRF and SR-XAS study of archaeological artefacts

AbstractWe report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as “proto-majolica” pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples’ speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent. FigureFe K-edge XANES spectra of selected proto-majolica samples and reference compounds (FeO, Fe3O4, Fe2O3, Fe+SiO2). D pigmented, L not pigmented.

The Use of FTIR and Micro-FTIR Spectroscopy: An Example of Application to Cultural Heritage

Micro-FTIR and FTIR spectroscopy is useful for the study of degradation forms of cultural heritage. In particular it permits to identify the degradation phases and to establish the structural relationship between them and the substratum. In this paper, we report the results obtained on marble from a Roman sarcophagus, located in the medieval cloister of St. Cosimato Convent (Rome), and on oolitic limestone from the facade of St. Giuseppe Church in Syracuse (Sicily). The main components found in the samples of both monuments are: gypsum, calcium oxalate, and organic matter due to probably conservation treatments. In particular, the qualitative distribution maps of degradation products, obtained by means of micro-FTIR operating in ATR mode, revealed that the degradation process is present deep inside the stones also if it is not visible macroscopically. This process represents the main cause of crumbling of the substrate. The results of this research highlight the benefits of the 𝜇-FTIR analysis providing useful insights on the polishing and consolidation processes of stone materials.

X-Ray Map Analyser

A new semi-automated image processing procedure based on multivariate statistical analysis of X-ray maps of petrological and material science interest has been developed to generate high contrast pseudo-coloured images highlighting the element distribution between and within detected mineral phases.This new tool package, developed in Python and integrated with ArcGis?, generates in only a few minutes several graphical outputs useful for classifying chemically homogeneous zones as well as extracting quantitative information through the statistical data handling of X-ray maps. The code, largely based on the use of functions implemented in ArcGis? 9.3 equipped with Spatial Analyst and Data Management licences, has been suitably integrated with original cyclic functions that hugely reduce the time taken to complete lengthy procedures. In particular these tools, after the acquisition of any kind of multispectral images allow fast and powerful data processing for efficient illustration and documentation of key compositional and microtextural relationships in rocks and materials. Display Omitted

Petrology and Geochemistry of Cretaceous Sedimentary Rocks of the Monte Soro Unit (Sicily, Italy): Constraints on Weathering, Diagenesis, and Provenance

The mineralogy and chemical compositions of shale and sandstone alternations of Cretaceous age of the Monte Soro Unit, Sicily, have been determined. The clay minerals in the shales are mostly illite and I-rich mixed-layer I/S reflected by enrichment in Al2O3, K2O, and chemically similar elements. The sandstones are subarkose to quartz arenite. The shales and sandstones have upper-crustal rare earth element patterns, and except for K2O, they are depleted in alkaline and alkaline-earth elements as a result of intense weathering. The sandstone and shale mineralogy suggests a diagenetic history in which the sediments were subjected to temperatures in excess of 100°C, during which interaction between some minerals in the shales and sandstones took place. Thus, diagenetic quartz cementation and feldspar alteration in the sandstones and smectite illitization in the shales occurred together with the shales being a sink for potassium and the sandstones a sink for silicon. Negative europium anomalies ( between 0.45 and 0.87), (Gd/Yb)ch ratios (<2, except for sample C1), and Sc/Cr versus La/Y and La-Th Sc diagrams suggest that the sedimentary rocks were derived from post-Archean granitoid-like rocks in a tectonically stable area. In addition, the foliated fabrics of polycrystalline quartz grains and the abundant phyllite rock fragments indicate a provenance from metamorphic rocks. The study of several trace element ratios (Ti/Zr, Cr/Zr, Y/Ni, Cr/V, Zr/Th, La/Th, La/Th, Cr/Th, Zr/Hf, Zr/Yb, Yb/Hf, V/La, La/Yb) strongly supports a local derivation from the European paleomargin.

Nanocrystalline TiO2 coatings by sol–gel: photocatalytic activity on Pietra di Noto biocalcarenite

Self-cleaning photocatalytic coatings based on TiO2 nanoparticles obtained by sol–gel techniques at two different pH values (1.3–10.6) have been investigated on carbonatic stone. The selected material is the yellowish lithofacies of Palazzolo Formation calcarenite, commonly named Pietra di Noto, widely used in the Baroque monuments of the Noto Valley (Sicily, Italy). SEM–EDS, XRD and Raman investigations were carried out to characterize the TiO2 nanoparticles (mainly nanocrystalline anatase) obtained by the acid and basic nanosols and the corresponding coatings on pietra di Noto. To evaluate the effects of the treatments at two different pH values, changes in the stone color appearance, water absorption by capillarity and the behavior for salt crystallization were measured. The photocatalytic activity of the coatings was evaluated under UV irradiation, by monitoring methyl orange and methylene blue dye degradation as a function of time. The results highlight the compatibility of both treatments with respect to the properties of the calcarenite stone, showing no chromatic changes, no alteration of physical properties, an improvement in the resistance to salts crystallization and the good photocatalytic activity on both dyes. The experimental data suggest that the basic coating has to be preferred for carbonatic stones for its harmlessness and better performances in terms of self-cleaning action and protection against water and salts.Graphical AbstractSelf-cleaning photocatalytic coatings based on TiO2, obtained by sol–gel at two different pH values, are applied on Pietra di Noto carbonatic stone. TiO2 nanoparticles and coatings are characterized by SEM, XRD and Raman. The photocatalytic activity of the coatings is evaluated under UV irradiation, by monitoring methyl orange and methylene blue dye degradation as a function of time. The basic coating is suitable for carbonatic stones for its harmlessness and better performances in terms of self-cleaning action and protection against water and salts.

Garnet-spinel-pyroxenite xenoliths from Hyblean Plateau (South-eastern Sicily, Italy)

SummaryRare garnet-spinel pyroxenite xenoliths occur in some basaltic tuff-breccia levels of Miocene age from the Valle Guffari (Hyblean Plateau, Sicily), together with a number of spinel-bearing mantle xenoliths. The garnet-bearing pyroxenites may be divided into two groups (“a” and “b”) on textural and mineralogical bases. Garnet-bearing spinel websterites with a fully recrystallized texture represent the first group (a). Here the garnet (Py54.5 A1m32 Gr13.5), with a diffuse kelyphitic alteration, forms a reaction corona between coarse spinel grains and the in contact pyroxenes. The transition from the spinel-pyroxenite to the garnet-pyroxenite field may depend on isobaric cooling from higher (magmatic?) temperatures. Garnet-pyroxene geothermometry indicates that the last equilibration most probably occurred at P = 1.0 GPa (ca.), T = 750 °C (ca).The second lithotype (b) is an orthopyroxene-bearing garnet-spinel clinopyroxenite, exhibiting a complex texture. It consists of zones of coarse clinopyroxene grains enclosing euhedral spinel passing to zones where tiny rounded crystals of the same pyroxene and spinel are enclosed in relatively large patches of extensively kelyphitisized garnet (Py64.8 Alm25.6 Gr9.6). Garnet also occurs as inclusion-free grains up to 4 mm in diameter. P-T calculations give significantly higher values than for the former case (a). The origin of the b-type garnet may also depend on subsolidus reaction of spinel and pyroxenes after an isobaric cooling from still higher temperatures, but a primary magrnatic origin might also be possible, especially for the “granular” garnets.P-T estimates for both the pyroxenite types closely match a steady geotherm for 100 mW/m2 surface heat flow. Such a relatively intense heat flow may suggest the occurrence of huge masses of hot magma intruding the Hyblean lithospheric mantle and lower crust at different levels.ZusammenfassungSeltene Granat-Spinell-Pyroxenit-Xenolithe kommen in einigen basaltischen Tuff-Breckzien Horizonten miozänen Alters aus dem Valle Guffari (lblei-Plateau, Sizilien) zusammen mit einer Anzahl von Spinell-führenden Mantel-Xenolithen vor. Aufgrund textureller und mineralogischer Kriterien können die Granat-führenden Pyroxenite in zwei Gruppen („a” und „b”) unterteilt werden. Granat-führende Spinell-Websterite mit vollkommen rekristallisierter Textur repräsentieren die erste Gruppe („a”). Hier bildet Granat (Py54.5 Alm32 Gr13.5) mit einer diffusen kelyphitischen Umwandlung, einen Reaktionssaum zwischen grobkörnigem Spinell und Pyroxenen, mit denen er in Kontakt ist. Der übergang vom Spinell-Pyroxenit- zum Granat-Pyroxenit-Feld kann auf isobarische Abkühlung von höheren (magmatischen ?) Temperaturen zurückgehen. Granat-Pyroxen-Geothermometrie zeigt, dass die letzte Equilibrierung sehr wahrscheinlich bei P = 1.0 GPa (ca.), T = 750°C (ca.) erfolgte.Der zweite Typ von Granat-führenden Pyroxeniten ist ein („b”) Orthopyroxenführender Granat-Spinell-Klinopyroxenit, der komplexe Texturen zeigt. Er besteht aus Zonen von grobkörnigem Klinopyroxen mit Einschlüssen von idiomorphem Spinell, der in Zonen übergeht, wo kleine gerundete Kristalle des gleichen Pyroxens und Spinells in relativ große Bereiche von extensiv kelyphitisiertem Granat (Py64,8 Alm25,6 Gr9,6) eingeschlossen sind. Granat kommt auch als einschlußfreie Körner mit bis zu 4 mm Durchmesser vor. P-T Berechnungen geben wesentlich höhere Werte als für die Gesteine des Types („a”). Die Entstehung der b-Typ-Granaten kann auch durch Subsolidus-Reaktion von Spinell und Pyroxen nach isobarischer Abkühlung von noch höheren Temperaturen beeinflußt sein; ein primärer magmatischer Ursprung könnte auch möglich sein, besonders für die „körnigen” Granate.P-T Abschätzungen für beide Pyroxenit-Typen sind gut einer Geotherme für 100 mW/m2 Wärmefluß an der Oberfläche zuzuordnen. Ein solcher, relativ intensiver Wärmefluß könnte auf das Vorkommen von großen heißen Magmenkörpern hinweisen, die den lithosphärischen Mantel unter dem Iblei-Plateau und die untere Kruste in verschiedenen Niveaus intrudierten.

Small angle neutron scattering as fingerprinting of ancient potteries from Sicily "Southern Italy…

Small angle neutron scattering measurements have been carried out in order to investigate, in microdestructive way, the mesoscopic structure of a variety of potteries of relevance to cultural heritage coming from different Sicilian (Southern Italy) archeological sites belonging to the “Strait of Messina” area and dated back to 7th–3rd century B.C. Data have been compared with the mesoscopic parameters extracted for two series of clayey sediments typical of the Strait of Messina area and fired under controlled conditions. The observed agreement between the features of reference and archeological samples allowed us to estimate the maximum firing temperature of the latter. Information on the pore sizes was obtained by the use of the concept of fractal surface, and compared with porosimetry results.

A multi-technique approach for the determination of the porous structure of building stone

The complete knowledge of the porous structure of rocks is necessarily requested for the prediction of the damages induced by salt crystallization. Nevertheless, the geometric description of the porous structure is usually very difficult because of the variability of the size distribution of voids, ranging from nanometers to millimeters, which generally is not accessible by a single methodology. For this reason, a multi-technique approach was used here: the investigation at sub-micrometric dimensional scale (> 0.004 μm) was carried out by Hg intrusion porosimetry (MIP), whereas the study at the nanoscale required Small Angle Neutron Scattering (SANS) analysis. All the results were interpreted in the framework of a fractal model. The analyses were performed on limestones of different geological formations, cropping out in south-eastern Sicily and largely used as building stones in Baroque monuments of the Noto Valley (belonging to the UNESCO Heritage List).