Celestino Grifa

Archaeometric study on terra sigillata from Cales (Italy)

Mineralogical and petrographical studies on 23 ancient pottery fragments of terra sigillata from ancient Cales (today Calvi Risorta, Caserta) are here discussed. Stamps on pottery surfaces assigned the fragments to Cales and other Italian workshops acting in Arezzo and Northern Italy area between 1 st century B.C.-1 st century A.D., other stamped fragments have an uncertain provenance. The mineralogical and petrographical features of pastes have been detected using optical microscopy, X-ray diffraction, X-ray fluorescence, and DTA-DTG analyses. The geochemical comparisons among ceramics, production indicators of Calenian pottery (Black Glazed pottery spacers) and local clayey raw materials allowed to distinguish locally produced potsherds from imported ones. Moreover, the whole archaeological and archaeometric data set allowed to draw main technological aspects of a fine ware production much used on rich roman tables.

Thin walled pottery from Alife (Northern Campania, Italy)

The ancient town of Allifae (modern Alife) represents one of the most interesting settlements of the Northern Campania area and together with the ancient city of Cales , was a thriving production centre of pottery. Excavations carried out inside the city wall, near the south gate, the so called, Porta Fiume, unearthed a huge dump of thin-walled ware, where the most abundant forms were cups and beakers, decorated with grooves or rouletting. The dump has been dated late Augustan/Tiberian age and the thin-walled vessels found can be identified with similar wares from Allifae, Cubulteria, Caiatia and perhaps Neapolis. Horace in his Sermones (II, 8,39) cited the Allifana beakers (described as fictiles ac subtiles by a Horace scholiast) and they could possibly be identified with the thin-walled wares produced in Allifae. If this the case, then the thin-walled vessels produced in Allifae were known in Rome as early as the end of I century B.C. In order to investigate and characterize the Allifae thin-walled pottery, twenty-one samples were selected and mineralogical-petrographic analyses (OM, XRD, XRF and SEM/EDS) were carried out. The clayey raw material used was a low-CaO alluvial clayey deposit from the Middle Valley of the Volturno River. The potters probably handled the sediment by a levigation process in order to remove the coarser grains, and making the clay suitable to produce such thin walls. Comparison with other regional production of thin-walled pottery allowed us to strictly distinguish the Allifana beakers.

Production and circulation of thin walled pottery from the Roman port of Neapolis, Campania (Italy)

Seventeen samples of thin walled pottery from the Roman port of Neapolis (late II century B.C. - early III century A.D.) were studied in order to ascertain the type of clay and temper utilised, and their provenance. Seven samples of thin walled pottery from a homogeneous group (based on mineralogical and chemical characteristics) represent a local production of this ceramic class within the Neapolis area. This group was manufactured with a low-CaO clay, that probably derived from a weathered or alluvial deposit, together with reworked pyroclastic material (e.g., Sorrento area or Sebeto River plain) and volcanic sand from the Neapolitan area, containing both Somma-Vesuvius and Phlegraean Fields products. Two other fragments could be attributed to different Campanian production areas, such as the Pozzuoli area. Eight outlier fragments found in the port of Neapolis probably originate from extra regional production sites (e.g. southern Tuscany or the Arno valley).

The characterization of natural gemstones using non-invasive FT-IR spectroscopy: New data on tourmalines

Fourteen samples of tourmaline from the Real Museo Mineralogico of Federico II University (Naples) have been characterized through multi-methodological investigations (EMPA-WDS, SEM-EDS, LA-ICP-MS, and FT-IR spectroscopy). The samples show different size, morphology and color, and are often associated with other minerals. Data on major and minor elements allowed to identify and classify tourmalines as follows: elbaites, tsilaisite, schorl, dravites, uvites and rossmanite. Non-invasive, non-destructive FT-IR and in-situ analyses were carried out on the same samples to validate this chemically-based identification and classification. The results of this research show that a complete characterization of this mineral species, usually time-consuming and expensive, can be successfully achieved through non-destructive FT-IR technique, thus representing a reliable tool for a fast classification extremely useful to plan further analytical strategies, as well as to support gemological appraisals.

The combined use of steam-treated bentonites and natural zeolites in the oenological refining process

Abstract Industrial minerals, particularly bentonites, have long been used in treatments to improve the stability and shelf life of white wines. We evaluated a new combination of rocks and minerals, including steam-treated bentonites and natural zeolites (chabazite and phillipsite), to greatly reduce the risk of protein and tartaric instability of wines. Detailed mineralogical, chemical and electrokinetic studies of these materials were conducted using powder X-ray diffraction (PXRD), X-ray fluorescence (XRF), microporosimetry, BET surface-area analysis and zeta-potential measurements. Several model wine solutions containing Bovine Serum Albumin (BSA) were prepared to evaluate the oenological performance of the rock/mineral combinations. UV-VIS spectrophotometry and ion chromatography were used to evaluate the degree of wine stabilization from the protein and tartaric point of view. The experimental results showed that steam treatment modifies both the microporosity and external surface area of the bentonite. These changes in surface area, along with creation of hydrophobic surfaces, significantly modified the behaviour of the steam-treated bentonites, requiring an increase in the amount of material necessary to bring the protein content to required levels. An important benefit derived from the use of steam-treated bentonites is that the pre-mixing with water before addition to wine is not necessary, as the material is readily dispersed. Finally, the addition of natural zeolites effectively decreased the potassium content, thereby improving the tartaric stability of white wines. In addition, this procedure results in minimal waste, as the bentonite-zeolite mixture can be reused as soil amendments in agriculture.

The mafic alkaline volcanism of SW Madagascar (Ankililoaka, Tulear region): 40Ar/39Ar ages, geochemistry and tectonic setting

High-precision 40Ar/39Ar ages, major and trace element, and radiogenic isotope data are presented for the basanites and alkali basalts forming the southwesternmost monogenetic volcanic field in Madagascar. The volcanic rocks were erupted along fissure zones and aligned cones in a nearly flat area covered by the Cenozoic sediments of the Morondava basin. The high-precision 40Ar/39Ar ages constrain the beginning of the magmatism in the Ankililoaka area to about 12 Ma, significantly earlier than suggested by previously published K/Ar ages. The Ankililoaka basanites include primitive compositions (MgO >10 wt%, Ni >200 ppm and Cr >400 ppm), whereas other basanites and alkali basalts experienced limited removal of olivine, chromiferous spinel and clinopyroxene. Initial Sr and Nd isotope ratios of the basanites are 0.70343–0.70445 and 0.51279–0.51282, respectively. The Pb isotope compositions are in the ranges 206Pb/204Pb = 19.08–19.38, 207Pb/204Pb = 15.61–15.64 and 208Pb/204Pb = 39.1–39.4. The alkali basalts have similar 87Sr/86Sr, 143Nd/144Nd and 207Pb/204Pb, but slightly lower 206Pb/204Pb and 208Pb/204Pb than the basanites. The isotopic composition of the Ankililoaka rocks partially overlaps with that of the Cenozoic volcanic mafic rocks of northern Madagascar, and differs significantly from that of the mafic volcanic rocks of central Madagascar, which have lower 206Pb/204Pb and 207Pb/204Pb, and higher 87Sr/86Sr. Major and trace element systematics and geochemical modelling suggest that the Ankililoaka mafic alkaline rocks are low-degree melts of an incompatible element enriched peridotite source starting from depths where garnet is stable. Crustal contamination during ascent was insignificant. We argue that the genesis of the Ankililoaka alkaline magmas was triggered by melting an enriched, volatile-rich lithospheric mantle uplifted in the Cenozoic. Supplementary material: Analytical techniques, X-ray fluorescence whole-rock data, mineral compositions, 40Ar/39Ar dataset, mantle source modelling and figures showing volcanological features and thin sections are available at https://doi.org/10.6084/m9.figshare.c.4065743

Non-invasive FTIR spectroscopy: new preliminary data for the identification of mineralogical phases forming Cultural Heritage materials

This paper focuses on the application of external reflection Fourier Transform Infrared spectroscopy for the classification of some minerals commonly used as gemstones and mineral collection: quartz (colourless, tourmalinated and smoky varieties), calcite and aragonite.The results highlight the differences between reflectance and absorbance spectra, allowing a faster, cheaper and non-destructive approach for the identification of monocrystalline minerals.

Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial

Abstract The encapsulation and delivery of drugs often involves the use of expensive microporous materials, and we have investigated the potential for natural zeolites from the widespread volcanic formations of southern Italy as alternatives to these carriers. Surface-modified natural zeolites (SMNZs) with diverse micellar structures (patchy and complete bilayers) were obtained by using different cationic surfactants [cetylpyridinium chloride (CP-Cl), benzalkonium chloride (BC-Cl), hexadecyltrimethylammonium chloride (HDTMA-Cl), and bromide (HDTMA-Br) with phillipsite-rich tuff from the Campania region (southern Italy)]. Loading and release kinetics tests of sodium ibuprofen (IBU) were carried out with organo-phillipsite composites using Fourier transform infrared spectroscopy (FTIR) and thermal analysis coupled with evolved gas analysis (EGA). Results from these tests were mathematically modeled to evaluate IBU adsorption and release mechanisms. The maximum loaded amount of IBU was attained for organo-phillipsite modified with HDTMA-Br (PHB), which showed a complete bilayer micellar structure. Whenever a patchy bilayer micellar structure formed, the lowest adsorptions of IBU were observed. Equilibrium adsorption results were fit using Langmuir, Sips, and Toth models. Pseudo-first-order and pseudo-second-order fits to the loading kinetic data provided significant goodness of fit. Good fits to the release kinetic data were obtained using first-order and Weibull equations, shedding new light on the release mechanism of IBU from phillipsite. The active amount of IBU on the modified zeolite surface was almost totally available for pharmaceutical purposes.