Phillipsite and Al-tobermorite mineral cements produced through low-temperature water-rock reactions in Roman marine concrete

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

Phillipsite and Al-tobermorite mineral cements produced through low-temperature water-rock reactions in Roman marine concrete

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

Use of zeolite-rich rocks and waste materials for the production of structural lightweight concretes

This paper aims at testing the use of mixtures constituted by natural zeolitized products and SiC-bearing industrial wastes (sludge deriving from polishing of porcelain stoneware tiles, hereafter DPM) for the production of lightweight expanded aggregates as constituents of structural and/or thermo-insulating lightweight concretes. Two commercial products have been used as zeolite natural source: Cab70 (Yellow facies of Campanian Ignimbrite) and IZclino (Turkish clinoptilolite-rich epiclastite). Different amounts of a calcareous material (Pozzano limestones - hereafter CP) from the Sorrento peninsula (Naples - Italy) were also added to a Cab70 - DPM mixture. All raw materials were characterized by means of mineralogical (XRPD) and chemical (XRF) analyses. All the products and mixtures were tested from a technological point of view by means of fusibility and firing tests in order to evaluate the expanding properties. It was evidenced that the expansion of the mixture was deeply depending on the occurrence of SiC in the industrial waste. The addition of CP (10 wt.%) to the mixtures accounts for an even increased expansion, though this is accompanied by a worsening of the mechanical features of the material. These results along with literature data allowed to select 3 mixtures (70% Cab70-30% DPM, 70% IZclino-30% DPM, 60% Cab70-30% DPM-10% CP) and each of them was used for the preparation of 5 l of lightweight aggregates afterward employed for the manufacture of lightweight concretes. It was remarked that natural zeolitized materials mixed with DPM (30 wt. %) can provide lightweight aggregates with densities ranging between 0.8 and 1.0 g/cm3 suitable for the preparation of structural lightweight concretes. The addition to the mixture of CP (10 wt.%) produces less dense aggregates (0.6-0.7 g/cm3) potentially useful for the manufacture of thermo insulating lightweight concretes

New Insights of Historical Mortars Beyond Pompei: The Example of Villa del Pezzolo, Sorrento Peninsula

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

Lava stones from Neapolitan volcanic districts in the architecture of Campania region, Italy

Abstract Results of a research carried out on the lavas from Campi Flegrei and Somma-Vesuvius volcanic districts are reported here. The lavas have been widely employed, since Roman age, in several important monumental buildings of the Campania region, mainly in the town of Naples and in its province. They are classified as trachytes (Campi Flegrei products), tephri-phonolites and phono-tephrites (Somma-Vesuvius complex) from a petrographical point of view. Sampling was carried out from well-known exploitation districts. A substantial chemical difference between the products of the two sectors was confirmed, while petrophysical characterization evidenced similarity among the two different materials, although some differences were recorded even in samples coming from the same exploitation site

Biotic, mineralogical, petrographic, and geomorphological characterization of the Falerno-Domitio shoreline (Campania region, southern Italy), with implication for environmental health studies: preliminary results

We report the first results of an ongoing study related to the project FARO (i.e. the Italian “Fund for original research projects”, granted by the Università di Napoli Federico II and IMI bank partner). This research project aims to the enhancement of the physical and biotic features of the coastal landscape related to the Falerno-Domitio shoreline, located in the mid-north coast of the Campania region (southern Italy), from the Garigliano river and Torregaveta. In the national scenario, this area can be considered as a valuable “natural laboratory”, for its wildlife (i.e. the Natural Reserve Foce Volturno, the Regional Park of Campi Flegrei, etc.), famous archaeological sites (i.e. Cuma excavations), and peculiar geological and volcanological characteristics (i.e. Phlegraean Fields). Unfortunately, it also suffers for a strong pollution and environmental degradation due to human activities. The research consists of a multidisciplinary analysis, mainly based on a bathymetric sensing, sampling of both the sea bottom sediments and the beach sands; it comprises: 1) integrated monitoring of the quality of environmental health through a biological study, 2) geomorphological and sedimentological analyses of the area and of the whole sample sets, with GIS data processing, 3) taxonomic and ecological analyses of selected benthic meiofauna assemblages, 4) mineralogy, petrography and geochemistry of beach sands along the shoreline, as well as of sea bottom samples. A complete sampling work of the beach sands, from the Garigliano estuary to the Cuma site, has been done, and the results of mineralogical, petrographic and chemical features, mainly in relation to major and trace elements data, as well as the granulometric curves, are presented. The ecologic and eco-toxicological studies are also carried out on selected samples, revealing the structure of meiofauna (benthic foraminifers and ostracods) assemblages. Tests on the occurrence of the bio-indicator organism Artemia salina have also performed, showing a relatively low toxicity of the samples analysed up to now. Preliminary bathymetric data are also presented

SUSTAIN drilling at Surtsey volcano, Iceland, tracks hydrothermal and microbiological interactions in basalt 50 years after eruption

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 192 m below the surface, were drilled using filtered, UV-sterilized seawater circulating fluid to minimize microbial contamination. These cores parallel a 181 m 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 181 m 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 354 m measured depth, provides further insights into eruption processes, including the presence of a diatreme that extends at least 100 m 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