3D fractures analysis and conservation assessment of wrought iron javelin through advanced non-invasive techniques.

3D imaging is a powerful tool of high resolution and non-destructive imaging technology for the study of ancient weapons and military technology, which reveals the original microstructures and corrosion patterns that threaten these artefacts. Here we report quantitative analysis of the 3D distribution and the orientation of fractures, and uncorroded metal particles within a wrought iron javelin unearthed at the Phoenician-Punic site of Motya, Italy. The study aimed to gain a better understanding of the relationship between corrosion and local stresses within the artifact and to evaluate its manufacturing technology, as well as the effects of post-treatment with Paraloid B72 on concretion and mineralized layers. The cracks were quantified in terms of content, size, and orientation. The condition of artefact storage was evaluated by a multi-analytical approach, including X-ray microscopy, field emission electron microscopy and micro-Raman spectroscopy. The results indicated that a specific technique was used to create a sturdy, lightweight javelin with a central shaft for piercing or thrusting. The fractures appear elongated in the direction of the longitudinal axis of the blade, showing the forging direction of the original metallic block. The study concluded that the artifact had not yet been stabilized due to the presence of lepidocrocite.

A comprehensive strategy for exploring corrosion in iron-based artefacts through advanced Multiscale X-ray Microscopy.

The best strategy to tackle complexity when analyzing corrosion in iron artefacts is to combine different analytical methods. Traditional techniques provide effective means to identify the chemistry and mineralogy of corrosion products. Nevertheless, a further step is necessary to upgrade the understanding of the corrosion evolution in three dimensions. In this regard, Multiscale X-ray Microscopy (XRM) enables multi-length scale visualization of the whole object and provides the spatial distribution of corrosion phases. Herein, we propose an integrated workflow to explore corrosion mechanisms in an iron-nail from Motya (Italy) through destructive and non-destructive techniques, which permit the extraction of the maximum information with the minimum sampling. The results reveal the internal structure of the artefact and the structural discontinuities which lead the corrosion, highlighting the compositional differences between the tip and the head of the iron nail.

Valorization of Eggshell Biowaste for Sustainable Environmental Remediation.

The management of large amounts of eggshell waste annually produced in the world is problematic as generally this material is only disposed at landfills with odor production and microbial growth. On the contrary, significant environmental and economic advantages could be obtained transforming this biowaste into new value-added products. Eggshell biowaste was the starting material for the synthesis of hydroxyapatite by a simple and sustainable procedure and applied for the removal of Co2+ from aqueous solutions. The effects of contact time and initial metal concentration were investigated in batch experiments. Eggshell-based hydroxyapatite (ESHAP) before and after Co2+ removal was characterized by X-ray diffraction and scanning electron microscopy. The process was rapid and reached equilibrium within 80 min. The removal efficiency was in the range 70-80% which is generally higher than other waste-derived adsorbents. Adsorption of Co2+ on the surface of ESHAP particles and ion exchange with Ca2+ resulting in the formation of a Co-phosphate are the main mechanisms of the metal removal. The conversion of eggshell waste to a low-cost adsorbent for the treatment of metal contaminated waters could contribute to a more sustainable and effective management of this biowaste.

Microstructure and chemical composition of Roman orichalcum coins emitted after the monetary reform of Augustus (23 B.C.).

A collection of ancient Roman orichalcum coins, i.e., a copper-zinc alloy, minted under the reigns from Caesar to Domitianus, have been characterised using scanning electron microscopy (SEM-EDS) and electron microprobe analysis (EMPA). We studied, for the first time, coins emitted by Romans after the reforms of Augustus (23 B.C.) and Nero (63-64 A.D). These coins, consisting of asses, sestertii, dupondii and semisses, were analysed using non- and invasive analyses, aiming to explore microstructure, corrosive process and to acquire quantitative chemical analysis. The results revealed that the coins are characterized by porous external layers, which are affected by dezincification and decuprification processes. As pictured by the X-ray maps, the elemental distribution of Cu and Zn shows patterns of depletion that in some cases penetrate in deep up to 1 mm. The composition of the un-corroded nucleus is a Cu-Zn alloy containing up to 30% of Zn, typical of coins produced via cementation process.

FIB-FESEM and EMPA results on Antoninianus silver coins for manufacturing and corrosion processes.

A set of ancient Antoninianus silver coins, dating back between 249 and 274 A.D. and minted in Rome, Galliae, Orient and Ticinum, have been characterized. We use, for the first time, a combination of nano-invasive (focused ion beam-field emission scanning electron microscopy-X-ray microanalysis (FIB-FESEM-EDX), voltammetry of microparticles (VIMP)) and destructive techniques (scanning electron microscopy (SEM-EDX) and electron microprobe analysis (EMPA)) along with non-invasive, i.e., micro-Raman spectroscopy. The results revealed that, contrary to the extended belief, a complex Ag-Cu-Pb-Sn alloy was used. The use of alloys was common in the flourishing years of the Roman Empire. In the prosperous periods, Romans produced Ag-Cu alloys with relatively high silver content for the manufacture of both the external layers and inner nucleus of coins. This study also revealed that, although surface silvering processes were applied in different periods of crisis under the reign of Antoninii, even during crisis, Romans produced Antoninianus of high quality. Moreover, a first attempt to improve the silvering procedure using Hg-Ag amalgam has been identified.

Archaeometric analysis of Roman bronze coins from the Magna Mater temple using solid-state voltammetry and electrochemical impedance spectroscopy.

Voltammetry of microparticles (VMP) and electrochemical impedance spectroscopy (EIS) techniques, complemented by SEM-EDX and Raman spectroscopy, were applied to a set of 15 Roman bronze coins and one Tessera from the temple of Magna Mater (Rome, Italy). The archaeological site, dated back between the second half and the end of the 4th century A.D., presented a complicated stratigraphic context. Characteristic voltammetric patterns for cuprite and tenorite for sub-microsamples of the corrosion layers of the coins deposited onto graphite electrodes in contact with 0.10 M HClO4 aqueous solution yielded a grouping of the coins into three main groups. This grouping was confirmed and refined using EIS experiments of the coins immersed in air-saturated mineral water using the reduction of dissolved oxygen as a redox probe. The electrochemical grouping of coins corroborated the complex stratigraphy of the archaeological site and, above all, the reuse of the coins during the later periods due to the economic issues related to the fall of the Roman Empire.

The thermal behaviour and structural stability of nesquehonite, MgCO3.3H2O, evaluated by in situ laboratory parallel-beam X-ray powder diffraction: New constraints on CO2 sequestration within minerals.

In order to gauge the appropriateness of CO(2) reaction with Mg chloride solutions as a process for storing carbon dioxide, the thermal behaviour and structural stability of its solid product, nesquehonite (MgCO(3).3H(2)O), were investigated in situ using real-time laboratory parallel-beam X-ray powder diffraction. The results suggest that the nesquehonite structure remains substantially unaffected up to 373 K, with the exception of a markedly anisotropic thermal expansion acting mainly along the c axis. In the 371-390 K range, the loss of one water molecule results in the nucleation of a phase of probable composition MgCO(3).2H(2)O, which is characterized by significant structural disorder. At higher temperatures (423-483 K), both magnesite and MgO.2MgCO(3) coexist. Finally, at 603 K, periclase nucleation starts and the disappearance of carbonate phases is completed at 683 K. Consequently, the structural stability of nesquehonite at high temperatures suggests that it will remain stable under the temperature conditions that prevail at the Earth's surface. These results will help (a) to set constraints on the temperature conditions under which nesquehonite may be safely stored and (b) to develop CO(2) sequestration via the synthesis of nesquehonite for industrial application.

Synthesis of nesquehonite by reaction of gaseous CO2 with Mg chloride solution: its potential role in the sequestration of carbon dioxide.

In this paper is reported a novel method to synthesize nesquehonite, MgCO(3) x 3H(2)O, via reaction of a flux of CO(2) with Mg chloride solution at 20+/-2 degrees C. The reaction rate is rapid, with carbonate deposition almost complete in about 10 min. The full characterization of the product of synthesis has been performed to investigate its potential role as a "CO(2)-sequestering medium" and a means of disposing Mg-rich wastewater. We investigated the nesquehonite synthesized using SEM, XRD, FTIR and thermal analysis. The thermodynamic and chemical stability of this low-temperature hydrated carbonate of Mg and its possible transformation products make our method a promising complementary solution to other methods of CO(2) sequestration. Carbonation via magnesium chloride aqueous solutions at standard conditions represents a simple and permanent method of trapping CO(2). It could be applied at point sources of CO(2) emission and could involve rejected brine from desalination plants and other saline aqueous wastes (i.e., "produced water"). The likelihood of using the resulting nesquehonite and the by-products of the process in a large number of applications makes our method an even more attractive solution.