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International audience; This research is part of the PON (Programma Operativo Nazionale) SINAPSIS (SIstema NAzionale Protezione SIti Sensibili), an interdisciplinary project combining archaeological and archaeometric methods. This paper focuses on frescoes from one of the 70 funeral monuments belonging to "Porta Mediana" Necropolis, a very interesting archaeological context located in Cuma, dating back to the first half of the 3rd century BCE. The study provided detailed information on pigments and colors acquired both on untreated and treated (restored) frescoes. Portable colorimetry and chemical-mineralogical (Raman spectroscopy and X-ray powder diffraction-XRPD, respectively) analyses were performed in situ and on collected samples in order to: 1) identify pigments, raw materials and provenance, 2) point out possible color changes caused by conservative treatments and/or weathering. The identified palette is typical of the Roman period; it includes both single and mixtures of two or more pigments to obtain particular hues. Moreover, the identified raw materials, such as red and yellow ochres, green frit and Egyptian blue, clearly highlighted the choice to use raw materials from local sources. The use of expensive coloring materials also suggests that the mausoleum belonged to a family or a group of people with a high social status.

This research aims to deepen knowledge on geomaterials used in building operations of a very important monumental complex belonging to the "Porta Mediana" necropolis the archeological site of Cuma. The entire site counts 70 mausoleums among which, the one named "Sphinx complex" or A63, is particularly important. For its realization several geomaterials have been used. Analytical results were carried out from several techniques such as optical microscopy, microchemical and mineralogical-petrographical analysis, scanning electron microscopy with EDS and X-ray powder diffraction. This approach allows to clarify the provenance of natural geomaterials and also the technological processes involved in the production of artificial geomaterials (mortars, plasters, cocciopesto). Phlegrean tuffs, due to their easy workability and good mechanical features, were used mainly for masonries and for decorative function (a bas-relief of a "sphinx" for example). As far as artificial geomaterials are concerned, the use of a volcanic aggregate, was privileged too. Some examples of imported stones were also found: limestones and marbles, the first one implemented as a building material for cippi of the fence while the second one for prestigious coating elements. Results permitted to evaluate building techniques of the period and mainly the wide potential of Phlegrean fields' materials when used as a bulding stone. This research aims also to give important informations for restoring and conservative actions useful for mausoleums of the entire site.

Roman mortars from a mausoleum (named D46b) belonging to the archaeological site of Porta Mediana necropolis, in Cuma (Naples, Southern Italy) have been studied by means of petrographic, mineralogical and micro-chemical analyses. The aim of this research is to fill the knowledge gap regarding mortar-based materials used in Roman age within this wide archaeological site. Two typologies of mortars (bedding and coating) were collected from mausoleum’s masonry. They were lime-based with addition of pozzolanic materials, according to Vitruvius’ recipe. Raw materials, such as volcanic sand and limestones, mainly from local sources, were preferentially used as aggregate, both for great availability and good properties. As regard production techniques, the multi-layer feature of the coating mortars, once again shows the great knowledge of the building art. Each layer is the result of a precise choice, as shown by the differences both in texture and petrographic features. Data from detailed mortars characterization have infer the outstanding skill of Roman craftsmen, as already proved by extraordinary durability of buildings. The research was very useful not only to increase the knowledge of this ancient culture but also to planning conservative actions, that, through mortar reproduction or the research of suitable materials, can promote the safeguard of this invaluable heritage.

At Positano, the renowned town of the Amalfi coast (Salerno province), a Roman villa was found beneath the church of Santa Maria Assunta. It likely dates back to I century BC - I century AD (Julio-Claudian age) and belonged to the freedman Posides Claudi Caesaris, from whose the town might probably derive the name (Della Corte, 1936). The villae were prestigious residences disseminated as status symbol of the wealthy Roman people all around the coastal areas of the Campania region (i.e. Vesuvian villae; Maiuri, 1955. Guzzo & Guidobaldi, 2008). During the 79 AD eruption of the Vesuvius the residence was suddenly destroyed and covered by a volcanoclastic debris flow more than 10 m thick, composed of a mass of gray ashes with large amount of high-porosity welded pumices. During the Middle age, Benedictine monks built an abbey on the same site of the Posides’ villa, then transformed in the present church dedicate to the Virgin. At the beginning of the 2000, the Archaeological Superintendence started the recovery of the overlying Benedictine crypts and extended the excavation and recovery also downward to the villa remains. Inside the crypts it was possible to unearth, descending in the villa from tiles roof till to mosaic pavement, a luxurious triclinio. Imprints of holes related to large wood poles (now replaced with plaster casts), as well as fragments of the roof, coffered ceiling, doors and other wooden remains were found embedded in the volcanoclastic mud. Tuff walls are decorated with fine plasters, polychrome frescoes of excellent painters, with hippocampus, eagle poised upon a globe, Pegasus and Cupids. These lively compositions are basically made by some colors, like the “Pompeian” red, blue and yellow ochre. This work reports a preliminary archaeometric study of various artifacts from the Positano villa, represented by plasters, fresco fragments, tile and other materials. Small but representative samples of the different findings were analyzed, in order to reach our characterization scopes and to provide useful information on probable future restoration activities. The analytical techniques used for mineralogical and petrographic study are: optical and stereoscopic studies on thin sections, modal analysis, X-ray powder diffraction (XRPD), scanning electron microscopy analysis (SEM) and energy-dispersion X-ray spectroscopy (EDS). Data concerning the composition of the artifacts and manufacturing techniques will be reported and compared with the reference literature. Della Corte M. 1936. Posides Claudi Caesaris libertus – Positano da Posidetanum? Rivista Indo-greca-Italica, 20, 67-73 Guzzo P.G. & Guidobaldi M.P. 2007. Nuove ricerche archeologiche nell'area vesuviana (scavi 2003-2006). Atti Conv. Int. Roma 1-3 febbraio, L’Erma di Bretschneider, 629 p. Maiuri A. 1955. Le vicende dei monumenti antichi della costa amalfitana e sorrentina alla luce delle recenti alluvioni. Rend. Acc. Arch. Lett. Belle Arti Napoli, XXIX, 87-98.

Low-cost zeolitic rocks are promising substitutes for feldspathic fluxes in ceramic bodies, since their fusibility, scarce hardness and high CEC should improve grinding and sintering. Five large-scale Italian deposits with different mineralogy were characterised and used in porcelain stoneware bodies. Their behaviour during grinding, pressing, drying and firing was appraised in laboratory and compared with zeolite-free bodies. Zeolites increased the slip viscosity during wet grinding, causing a coarser grain size distribution and consequently some drawbacks in both unfired and fired tiles. Overcoming this hindrance by dry grinding of zeolitites, the technological behaviour of zeolite-bearing tiles appear to be similar to current porcelain stoneware, though with larger firing shrinkage and residual closed porosity.

Roman mortars from a mausoleum (named D46b) belonging to the archaeological site of Porta Mediana necropolis, in Cuma (Naples, Southern Italy) have been studied by means of petrographic, mineralogical and micro-chemical analyses. The aim of this research is to fill the knowledge gap regarding mortar-based materials used in Roman age within this wide archaeological site. Two typologies of mortars (bedding and coating) were collected from mausoleum’s masonry. They were lime-based with addition of pozzolanic materials, according to Vitruvius’ recipe. Raw materials, such as volcanic sand and limestones, mainly from local sources, were preferentially used as aggregate, both for great availability and good properties. As regard production techniques, the multi-layer feature of the coating mortars, once again shows the great knowledge of the building art. Each layer is the result of a precise choice, as shown by the differences both in texture and petrographic features. Data from detailed mortars characterization have infer the outstanding skill of Roman craftsmen, as already proved by extraordinary durability of buildings. The research was very useful not only to increase the knowledge of this ancient culture but also to planning conservative actions, that, through mortar reproduction or the research of suitable materials, can promote the safeguard of this invaluable heritage.

For this study, the rare Cu-bearing silicate fumarolic assemblages from the Somma–Vesuvius volcano, Italy, characterised by the rare mineral litidionite, CuKNaSi4O10, were investigated. We report new data about Cu- and Ti-bearing phases found in these mineralisations, in which Ti-bearing litidionite occurs together with kamenevite, perovskite and rutile. Ti-bearing litidionite appears on the latest stages of partial crystallisation of Ti-bearing silica glass. Incorporation of Ti4+ into the litidionite crystal structure was investigated in detail. The Raman spectra of Ti-bearing litidionite contains an intense band at 597 cm−1 related to anti-symmetric bending vibrations of Si‒O bonds or overlapping stretching vibrations of Ti‒O bonds. The bands in the range 350‒500 cm−1 correspond to symmetric bending vibrations of O‒Si‒O bonds and overlapping stretching vibrations of Ti‒O bonds. The crystal structure of Ti-litidionite has been refined in the P$\bar{1}$ space group, a = 6.9699(7), b = 7.9953(10), c = 9.8227(10) Å, α = 105.186(9), β = 99.458(8) and γ = 114.489(10) to R1 = 0.064 for 1726 unique observed reflections. The refinement of the site-occupation factors confirmed the presence of Ti at a five-coordinated M site. The mean bond distance of 2.125 Å for the M site agrees with its refined occupancy (Ti0.32Cu0.30Ca0.29Fe0.09)1.00. The incorporation of Ti into the litidionite structure is accompanied by the complex heteropolyhedral substitution according to the scheme VTi4+ + VII–VIII□ + IVAl3+ ↔ VCu2+ + VII-VIII(Na,K)+ + IVSi4+. Two possible configurations for the phase with maximal TiO2 content (12.06 wt.% or 0.56 Ti apfu) CuTiK□Na2Si7AlO20 (Z = 1) or CuTiK2Na□Si7AlO20 (Z = 1) have been proposed.

This research is based on the characterization of ancient mortars from the Anfiteatro Flavio (Pozzuoli) dating back to the 1st and 2nd century CE through a multi-analytical approach involving macroscopic, mineralogical, petrographic, and chemical investigations. The goal that has been set is to deepen knowledge about mortar mix design, the provenance of used raw materials, and secondary minerogenetic processes that have occurred within ancient Roman mortars. Results show that: (i) raw materials for mortar preparation have a local provenance, i.e., Phlegraean Fields area; (ii) mortars can be considered as hydraulic; (iii) calcite presence could be due to a non-complete calcination process, an improper slaking or to exposition of materials to the subaerial environment; (iv) gypsum is due to calcite sulfation process; (v) halite presence is due to marine aerosol exposition. The achieved information testifies that, for at least two centuries, Roman builders considered the identified mortar mix as optimal for their buildings, but also contributes to the understanding of their technical skills and represents an important first step to planning future restoration operations.

This paper focuses on the authigenic mineralization processes acting on “Tufo Rosso a Scorie Nere” (TRS), i.e. one of the main pyroclastic units of the Vico stratovolcano (Latium, Italy). The pyroclastic deposits appear in general massive and made of “black vitreous vesiculated juvenile scoriae”, immersed in an ashy matrix lithified after zeolitization processes. The main minerals are chabazite and phillipsite, and the zeolitic content is locally variable, reaching 68 % wt. Zeolites grow replacing both amorphous fraction and pre-existing phases, occurring inside both matrix and scoriae. Concerning scoriae, zeolitization moves from the rim to the core of the scoriaceous fragment as a function of (a) temperature of the fluids and (b) permeability (primary or secondary). Composition of parental fresh glass and that of zeolitized rocks is compatible with trachyte chemistry, lightly undersaturated in SiO2, and the alteration processes modified the parental rock chemical features. Zeolites genesis is ascribed to a “geoautoclave-like system”, and zeolites display a Si/Al ratio similar to that of the parental glasses. TRS presents promising mineralogical characteristics as supplementary cementitious material in the production of mixed cements.

In this work, four zeolite-bearing materials (three naturally occurring and one of synthetic origin) were considered for thermal energy capture and storage. Such materials can store thermal energy as heat of desorption of the water present therein, heat that is given back when water vapor is allowed to be re-adsorbed by zeolites. This study was carried out by determining the loss of water after different activation thermal treatments, the water adsorption kinetics and isotherm after an activation step of the zeolites, the intergranular and intragranular porosity, and the thermal conductivity of the zeolite-bearing materials. Moreover, the thermal stability of the framework of the zeolites of the four materials tested was investigated over a large number of thermal cycles. The results indicate that zeolite 13X was the most suitable material for thermal energy storage and suggest its use in the capture and storage of thermal energy that derives from thermal energy waste.

Publisher's version (útgefin grein), The 2017 Surtsey Underwater volcanic System for Thermophiles, Alteration processes and INnovative concretes (SUSTAIN) drilling project at Surtsey volcano, sponsored in part by the International Continental Scientific Drilling Program (ICDP), provides precise observations of the hydrothermal, geochemical, geomagnetic, and microbiological changes that have occurred in basaltic tephra and minor intrusions since explosive and effusive eruptions produced the oceanic island in 1963-1967. Two vertically cored boreholes, to 152 and 192m below the surface, were drilled using filtered, UV-sterilized seawater circulating fluid to minimize microbial contamination. These cores parallel a 181m core drilled in 1979. Introductory investigations indicate changes in material properties and whole-rock compositions over the past 38 years. A Surtsey subsurface observatory installed to 181m in one vertical borehole holds incubation experiments that monitor in situ mineralogical and microbial alteration processes at 25-124 °C. A third cored borehole, inclined 55° in a 264° azimuthal direction to 354m measured depth, provides further insights into eruption processes, including the presence of a diatreme that extends at least 100m into the seafloor beneath the Surtur crater. The SUSTAIN project provides the first time-lapse drilling record into a very young oceanic basaltic volcano over a range of temperatures, 25-141 °C from 1979 to 2017, and subaerial and submarine hydrothermal fluid compositions. Rigorous procedures undertaken during the drilling operation protected the sensitive environment of the Surtsey Natural Preserve., Funding for this project was provided by the International Continental Scientific Drilling Program (ICDP) through a grant to the SUSTAIN project (led by Marie D. Jackson); a grant of excellence from the Icelandic Research Fund, ICFRANNÍS (the IceSUSTAIN consortium led by Magnús T. Gudmundsson); the Bergen Research Foundation and K.G. Jebsen Centre for Deep Sea Research at the University of Bergen, Norway (led by Steffen Leth Jørgensen); the German Research Foundation (DFG) (led by Wolfgang Bach and Bernd Zimanowski); and DiSTAR, Federico II, University of Naples, Federico II, Italy (led by Piergiulio Cappelletti). The University of Utah, USA (Marie D. Jackson), and the two Icelandic power companies Reykjavík Energy and Landsvirkjun contributed additional funds. In kind support by several Icelandic institutions and companies contributed greatly to the success of the project, as did the dedicated work of several volunteers. The logistical support provided by the Icelandic Coast Guard was instrumental in carrying out the drilling operation. Norðurflug Helicopters and the Vestmannaeyjar Rescue Group provided critical logistical support. Jeremy Fisher and Rowan McGuire contributed to this article. The DOSECC drilling team, Steve Cole, Justin Blouin, A. J. Vecchiarelli, Matthew Lyon, and Michael Vinson, did excellent work. Hjalti Franzson provided guidance, and Þorsteinn Jónsson, Bjarni Kristinsson, Gísli Sighvatsson, and Sveinbjörn Steinþórsson contributed to the logistical operation on Surtsey. Unpublished borehole temperature measurements were made during the annual Surtsey Research Society expedition in July 2018.

A Roman luxury villa (1st century BC) was discovered in the town of Positano, in the Sorrento peninsula (Campania region, southern Italy). Despite being more than 20 km away from Vesuvius, the villa was buried under almost overall 20 meters (total thickness) of pyclastic materials of the Plinian eruption of 79 AD, which destroyed Pompeii and Herculaneum towns. The exceptional level of conservation of this residential complex is due to the peculiar burial process, which determined the excellent state of preservation of both the fresco decorations (Fourth Style) and all other artefacts (masonries, plasters, tiles, furnishing remains, wooden elements, kitchenware, glazed oil lamps, bronze vessels and other metallic findings, etc.). This study presents the results of a multi-analytical archaeometric analysis of plasters, fresco pigments and roof tiles, aimed at identifying their mineralogical and petrographic nature and the provenance of raw materials. Constraints to the geoarchaeological landscape of the Positano area are also given. The analyzed plasters are mainly lime-based, usually with the addition of an aggregate. The anchoring layer is made by a volcanic component, characterized by clinopyroxene, alkali feldspar, garnet, amphibole, biotite and leucite crystals, together with a sedimentary component represented by carbonatic fragments, also with traces of microfossils. The features of plasters confirm the high degree of technological standardization of plasters in classical Roman age. Mineral pigments recognized by preliminary XRD are mainly iron-based for the ochers-red-crimson colors and copper-based for green-blues colors. In the roof tiles two kind of tempers are identified. In three samples a volcanic temper was identified, and represented by clinopyroxene, feldspar, garnet and leucite, whereas the temper of a fourth sample contained pumices with minor amounts of alkali feldspar, clinopyroxene and biotite. The raw materials are of local provenance (Somma-Vesuvius, Phlegraean Fields, Apennine limestones), and the microstructure of the materials are comparable with similar artefacts from Pompeii, Herculaneum and other Roman sites in Campania region. On the basis of geoarchaeological investigations, here reported, it is reasonable to think that there are other unearthed archaeological areas in Positano that will require further study to be properly known

Zn-phyllosilicates are common minerals in nonsulfide Zn deposits and can give crucial information about the genesis of these oxidized mineralizations. They seldom represent the prevailing economic species but might have a significant impact on mineral processing. This study has been carried out on the Mina Grande and Cristal Zn-sulfide/nonsulfide deposits, which occur in the Bongará district (Amazonas region, northern Peru). The Cristal and Mina Grande orebodies are hosted by the sedimentary (prevailingly carbonate) successions of the Pucará Group (Condorsinga formation, Lower Jurassic), in an area affected by Neogene tectonics and characterized by Late Miocene and Pliocene-Early Pleistocene uplift phases (Andean and Quechua tectonic pulses). The Cristal deposit consists of both sulfide (sphalerite with minor pyrite and galena) and nonsulfide concentrations. The nonsulfides consists of smithsonite, hemimorphite, hydrozincite, chalcophanite, goethite, and greenockite, locally associated with Zn-bearing phyllosilicates. The Mina Grande deposit consists almost exclusively of Zn-oxidized minerals in limestone host rocks. The nonsulfides association consists of hydrozincite, hemimorphite, smithsonite, fraipontite, and Fe-(hydr)oxides, also containing a clayey fraction. The study deals with TEM-HRTEM and AEM investigations on clayey materials, to determine their crystal-chemical features and the origin of the complex Zn-clays-bearing parageneses. In both deposits, Zn-bearing illites (1Md and 2M polytypes) and I/S clay minerals (I3) are the main detected phases, with few compositions close to (Zn-bearing) muscovite. In the clayey fraction at Mina Grande, fraipontite, a Zn-bearing mica called K-deficient hendricksite, and (Zn-bearing) kaolinite also occur. Zn-illites and smectites (always containing Zn in variable amounts) characterize the mineral association at Cristal. The investigated compositional gap between di- and tri-octahedral Zn-phyllosilicates gives indications on the genetic relationships between them and advances on the knowledge of these species. The present work gives an insight into the Zn-bearing phyllosilicates systems by determining the amount/mode of metal incorporation in their lattices and understanding the relationships of natural occurring clay-rich complex associations, which can act as models for possible synthetic counterparts., This work was partly supported by Departmental funds 2017 (University of Napoli Federico II) granted to G. Balassone and by the research projects CGL201675679-P from the Spanish Government and the Research Group RNM-179 of the Junta de Andalucìa

The evolution of hydrothermal alteration in glassy and variably palagonitized tuff, erupted as tephra in 1963 – 1964 on Surtsey, an island built in the offshore extension of Iceland’s southeast rift zone, is documented through a comparative petrographic study of samples from drill cores recovered in 1979 and 2017. Time-lapse alteration within the low-temperature meteoric to seawater dominated hydrothermal system of the volcano is characterized in terms of secondary mineral contents, alteration rates and alteration style with depth. Between 1979 and 2017 palagonitization and cementation by secondary minerals has progressed into previously poorly altered parts of the system, leading to increased consolidation of the basaltic tephra. Alteration rates range between 1.05 – 42.5 μm∙yr-1 for palagonitization of glass and 0.4 – 8.33 μm∙yr-1 for pseudomorphic olivine replacement by clay minerals over a temperature interval of 47 – 140°C. Five distinct zones of alteration style, distinguished through alteration mineralogy, development of authigenic phases over time, as well as degree of alteration are described. Alteration of basaltic tephra at Surtsey volcano is defined by an early stage of phillipsite and clay mineral formation, followed by a later stage of analcime and tobermorite formation as well as replacement of phillipsite below the water table in zone 2 between 65.4 and 138.4 m. Only minor advancement of alteration is detected in zone 3 between 138.4 – 150.3 m depth, where the primary tephra remains largely unpalagonitized and unconsolidated. In contrast, from 1979 to 2017 alteration has increased between 150.3 – 177.8 m depth, in zone 4, leading to rapid and extensive glass and olivine alteration. The quantification of these time-lapse hydrothermal alteration processes at Surtsey provides an important reference for studies of the evolution of young oceanic islands hosting hydrothermal systems., International Continental Scientific Drilling Program (ICDP); Icelandic Research Fund, ICF-RANNÍS; Bergen Research Foundation and K.G. Jebsen Centre for Deep Sea Research at the University of Bergen, Norway; German Research Foundation; DiSTAR, Federico II, University of Naples, Federico II, Italy; University of Utah, USA; Reykjavík Energy; Landsvirkjun, Pre-print

This research provides a characterization of ancient Roman mortars from “Villa del Capo di Sorrento” (commonly known as “Villa di Pollio Felice” or “Bagni della Regina Giovanna”). A deepened analysis of cementitious binding matrix and aggregates was conducted with the aims of determining possible sources of raw materials and the mix recipe, and to evaluate the minerogenetic secondary processes. Twenty samples taken from the Villa were investigated by means of a multi-analytical approach, including polarized optical microscopy on thin sections, X-ray powder diffraction, scanning electron microscopy analysis, energy dispersed spectrometry, simultaneous thermal analyses, and mercury intrusion porosimetry. Bedding mortars were made with slaked lime mixed with volcanic materials, whereas coating mortars were made adding to previous recipe as ceramic fragments. All samples were classified as hydraulic mortars. Cementitious binding matrix was characterized by gel-like C-A-S-H, calcite, hydrocalumite, and gypsum, deriving from lime/pozzolanic material. Geomaterials used for mortar production had a local origin. Pozzolanic materials, such as volcanic fragments, scoriae, pumice, and crystal fragments derived from both pyroclastic rocks of the Campi Flegrei district and from rocks of the Somma-Vesuvio complex, porosity test suggest that the products related to minerogenetic secondary processes, make mortars more resistant.

Incorporation of diclofenac sodium into phillipsite modified with cetylpyridinium chloride (CP-Cl) or hexadecyltrimethyl ammonium bromide (HDTMA-Br) was followed by batch equilibrium adsorption studies in buffer solution at pH = 7.4. Characteristics of the drug/surfactant/zeolite complexes were investigated by UV/VIS, FTIR spectroscopy, thermal (DTA/TG) analysis and ζ-potential measurements. The obtained data confirmed that organic cations at phillipsite surface were responsible for incorporation of diclofenac sodium. Diclofenac sodium incorporated amounts increased with increasing the amount of each surfactant as well as with increasing the initial drug concentration. Langmuir model was the best model for fitting the experimental data of diclofenac adsorption on surfactant/phillipsite composites, suggesting complex adsorption mechanism. The physico-chemical properties of surfactant/phillipsite composites and enhanced incorporation of diclofenac sodium suggests that it might be possible to use these materials as drug carriers.

The topic of this study is the archaeometric characterization of mortars from Villa del Pezzolo, a Roman Villa located in Seiano (Napoli-Campania, Italy), dated between the 1st century B.C. and the 3rd century A.D. Mortars were analyzed by means of a multi-analytical approach (polarized optical microscopy, X-ray powder diffraction, scanning electron microscopy and energy-dispersed spectrometry, thermal analyses and mercury intrusion porosimetry) according to existing recommendations. Analytical results evidenced the use of local geomaterials composed of sedimentary and volcanic aggregates in the mix design and confirmed the three distinct building phases identified by archaeologists. Volcanic tuff fragments, identified in the 1st building phase can be ascribed to Campanian Ignimbrite formation, widely cropping out in the Sorrento Peninsula, as confirmed by the presence of glassy shards, partially devitrified and replaced by authigenic feldspar, a typical feature of welded grey ignimbrite lithofacies (WGI). Volcanic aggregates in samples of the 2nd and 3rd building phases show, instead, the presence of leucite-bearing volcanic scoriae and garnet crystal fragments related to Somma-Vesuvius products. Study of these mortars allowed us to: (1) understand the production technologies, (2) highlight use of materials with hydraulic behavior, such as volcanic and fictile fragments, (3) confirm the three building phases from compositional features of mortars and (4) highlight the change over time of the volcanic aggregate for mortars mix-design.

Author(s): Jackson, MD; Mulcahy, SR; Chen, H; Li, Y; Li, Q; Cappelletti, P; Wenk, HR | Abstract: Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash (pulvis) "that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass (fierem unum lapidem), impregnable to the waves and every day stronger" (Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al3+ substitution for Si4+ in Q3 tetrahedral sites, and suggest coupled [Al3++Na+] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.

Campi Flegrei is a large volcanic area situated northwest of Naples, Italy. Two archeological sites, the Sybil's Cave and the Piscina Mirabilis, are artificial caves dug in the yellow tuff and used during antiquity for various purposes. This paper describes for the first time the algal biodiversity of these caves and determines whether environmental factors such as light intensity and humidity are influential in species distribution. A total of twenty-two algal species were identified by molecular methods (18S rDNA); the largest group was Cyanobacteria (eleven species), followed by algae Chlorophyta (six), Rhodophyta (two) and Bacillariophyta (two). Cluster analysis of algal distribution in the caves in relation to light and humidity showed no relevant differences in algal distribution between the two caves. Three different algal groups were identified. The first one includes strains strictly dependent on low humidity, a second cluster was mainly associated with sites where humidity is not a severe constraint, and a third group, mainly represented by filamentous cyanobacteria, is probably dependent on high humidity, since it was detected only at Piscina Mirabilis.

A new International Continental Drilling Program (ICDP) project will drill through the 50-year-old edifice of Surtsey Volcano, the youngest of the Vestmannaeyjar Islands along the south coast of Iceland, to perform interdisciplinary time-lapse investigations of hydrothermal and microbial interactions with basaltic tephra. The volcano, created in 1963–1967 by submarine and subaerial basaltic eruptions, was first drilled in 1979. In October 2014, a workshop funded by the ICDP convened 24 scientists from 10 countries for 3 and a half days on Heimaey Island to develop scientific objectives, site the drill holes, and organize logistical support. Representatives of the Surtsey Research Society and Environment Agency of Iceland also participated. Scientific themes focus on further determinations of the structure and eruptive processes of the type locality of Surtseyan volcanism, descriptions of changes in fluid geochemistry and microbial colonization of the subterrestrial deposits since drilling 35 years ago, and monitoring the evolution of hydrothermal and biological processes within the tephra deposits far into the future through the installation of a Surtsey subsurface observatory. The tephra deposits provide a geologic analog for developing specialty concretes with pyroclastic rock and evaluating their long-term performance under diverse hydrothermal conditions. Abstracts of research projects are posted at http://surtsey.icdp-online.org.

Slow-moving landslides affect several areas in the Apennine chain (Italy). They involve sedimentary rocks that are weathered in the more surficial parts. The occurrence of weathering-related clay minerals (e.g. smectites) able to trap high amounts of water is generally considered a predisponding factor for these landslides. The main goal of this research is to verify this statement, carrying out a mineralogical-geotechnical characterization of clayey rocks occurring in the Termini Nerano slow-moving landslide (Massalubrense, Italy). The mineralogical composition of soils involved in the landslide was evaluated on several drill-core samples from the studied area, by using quantitative X-ray powder diffraction analyses, calibrated through chemical bulk rock analyses. Clay separates allowed to determine the composition of the clay fraction. The results confirm that the total amount of clays, and specifically the smectite amount in mixed layers I/S, could have played a role in the landslide development. However, relationships between mineralogical composition and weathering zones in the soil have not been observed. Geotechnical analyses attested that the mechanical behavior of the material involved in the landslide depends on the amount of granulometric clay fraction in the samples, but, differently from what expected, no correlations were observed between this behavior and the measured amounts of smectite or mixed layers I/S.