Sedimentological, mineralogical and geochemical features of late quaternary sediment profiles from the Southern Tuscany Hg Mercury District (Italy): Evidence for the presence of pre-industrial mercury and arsenic concentrations

Southern Tuscany (Italy) is an important metallogenic district that hosts relevant S-polymetallic deposits that have intensely been exploited for centuries. Consequently, potential toxic elements, such as Hg and As, are widely distributed in the surrounding environment. In this paper, an extensive sedimentological, mineralogical and geochemical study of two Late Quaternary sediment profiles, partially outcropping along the coast of southern Tuscany (Ansedonia area), was carried out to evaluate the contents and mobility of Hg and As with the aims to contribute to the definition of the geochemical baseline of southern Tuscany before the human intervention and evaluate the potential dispersion of these harmful elements. The sedimentological, mineralogical and geochemical (major elements) features revealed that the studied profiles are mostly related to the local geological characteristics and the Quaternary geological history of the area. The concentrations and the normalized patterns of trace and rare earth elements highlighted the absence of any anthropogenic activity. This implies that the studied samples are to be regarded as good proxies for evaluating the geochemical baseline of southern Tuscany before the intense mining activity. The enrichment factors (EF) of most trace elements were indeed lower or close to 2, indicating a variability close to the average concentration of the Upper Continental Crust (UCC), while other elements slightly enriched, such as Pb, were in agreement with the natural baseline reported for southern Tuscany. Mercury and As displayed EF values >40 when compared to the average contents of UCC, although they decrease down to 4 when compared to the suggested baseline for southern Tuscany. The higher Hg and As contents detected in this study, inferred to natural sources, evidenced (i) the great natural variability occurring in largely mineralized areas and (ii) the importance of estimating reference environmental parameters in order to avoid misleading interpretations of the detected anomalies. Moreover, the results of leaching test on sediment samples denoted a relatively low mobility of Hg and As, suggesting that these elements are preferentially mobilized by transport of clastic sediments and such anomalies may be preserved for relatively long times in Quaternary sediments. However, leachable Hg (0.6-9.7 μg/L) and As (2.1-42.2 μg/L) concentrations are significantly high when compared to those of the Italian limit for groundwater (1 μg/L for Hg and 10 μg/L for As). Quaternary sediments from southern Tuscany could then be a potential, though natural, source of Hg and As to groundwater systems

A new approach to non-linear multivariate calibration in laser-induced breakdown spectroscopy analysis of silicate rocks

In this paper a new approach to quantitative Laser-Induced Breakdown Spectroscopy (LIBS) analysis of silicate rocks is presented. The method is adapted from the Franzini and Leoni algorithm, a method widely used in X-Ray Fluorescence analysis for correcting the matrix effects in the determination of the composition of geological materials. To illustrate the features of the new method proposed, nine elements were quantified in 19 geological standards by building linear univariate calibration curves, linear multivariate calibration surfaces (PLS) and using Artificial Neural Networks. The results were then compared with the predictions derived from the application of the algorithm here proposed. It was found that the Franzini and Leoni approach gives results much more precise than linear uni- and multivariate approaches, and comparable with the ones derived from the application of Artificial Neural Networks. A definite advantage of the proposed approach is the possibility of building multivariate non-linear calibration surfaces using linear optimization algorithms, a feature which makes the application of the Franzini and Leoni method in LIBS analysis much simpler (and controllable) with respect to the algorithms based on Artificial Neural Networks

Application of double-pulse micro-LIBS 3D compositional mapping to the analysis of ceramics

We developed a new Laser-Induced Breakdown Spectroscopy (LIBS) instrument for 3D compositional mappings of archaeological objects. The system, based on the Modì double-pulse instrument, allows the reconstruction of maps with lateral resolution up to 20 microns and sub-micron depth resolution

Provenance of white marbles from the Roman City of tauriana (Palmi, Reggio Calabria, Italy)

The work shows the results of an archaeometric study performed on fourteen white marble samples from the Roman city of Tauriana (Palmi, Reggio Calabria, Italy), belonging to different architectural elements of the Municipal Museum Complex and artifacts reused in the modern town. Samples were studied by optical microscopy (OM), x-ray powder diffraction (XRPD), and isotope ratio mass spectrometry (IRMS) of13C and18O with the aim to identify their provenance. The comparison between the collected data and the historical ones, concerning the ancient quarries of white marble of the Mediterranean area, allowed us to prove that most of the marbles used in the city of Tauriana were from the Apuan Alps Basin (Carrara) and, in few cases, from Minor Asia (Proconnesos, Aphrodisias, Docimium) and Greek (Thasos and Pentelic) quarries

Geochemical characterization of recent Nile Delta inner shelf sediments: Tracing natural and human-induced alterations into a deltaic system

The present study deals with the geochemical changes observed along Nile Delta inner shelf sediments over a period of 20 years (1995–2015). Major, minor, and trace constituents as well as rare earth elements (REE) were investigated in the surface sediments collected from seven transects along the inner shelf on five years intervals. Geochemical composition of sediments in Nile Delta inner shelf exhibits continuous changes over time due to the depositional and sediment transport processes. The sediments are generally enriched with Fe and Ti oxides, as well as Ta, Nb, Y in comparison to the Upper Continental Crust (UCC). These alterations signify the impact of processes such as erosion and sediment transport, as well as the impact of anthropogenic interferences such as damming the Nile River Flow. The reduction of the sediment input from the Nile River has somehow altered the geochemical signature of the inner shelf sediments. The REE patterns indicate weathering in areas subjected to erosion, while trace elements and major oxides spatial and temporal distributions concentrate eastwards under the influence of the easterly sediment transport pattern. Nile Delta inner shelf presented a typical case for understanding the link between geochemistry and sedimentary processes in nearshore and deltaic systems

Insight into summer drought in southern Italy: palaeohydrological evolution of Lake Pergusa (Sicily) in the last 6700 years

The Sicily region (central Mediterranean) is at high risk of drying and desertification caused by current warming and land management. The aim of this study is to place current climatic changes within the past trajectories and natural climatic variability of the Holocene. For this we re-examine a sediment core retrieved at Lake Pergusa covering the last ca. 6700 years. A multiproxy investigation, and in particular the oxygen isotope composition of lacustrine carbonate (delta O-18(c)), allowed us to reconstruct decadal- to centennial-scale hydrological changes. The wettest period occurred between ca. 6700 and 6000 cal a bp. The delta O-18(c) record indicates a new period of wetter conditions between ca. 3700 and 2400 cal a bp. In particular, a delta O-18(c) minimum between 2850 and 2450 cal a bp overlaps with the period of the 'Great Solar Minimum' and corresponds to a dramatic reduction of arboreal pollen (AP%) and to an increase in synanthropic pollen, marking the onset of Greek colonization in the region. The longest driest interval corresponds to the Medieval Climate Anomaly, whereas the highest delta O-18(c) values are recorded in the last 150 years. The trend of the last 3000 years suggests that, considering future climate projections, the area will experience unprecedented drying exacerbated by human impact

Archaeometric approach for studying architectural earthenwares from the archaeological site of s. Omobono (Rome-Italy)

This paper reports the findings of an archaeometric study performed on 14 architectural earthenwares from the archaeological site of S. Omobono, located in the historic center of Rome (Italy). The archaeological site, accidentally discovered in 1937, includes the remains of a sacred area previously occupied by two temples, one of which was converted into the church of S. Omobono, in 1575. The samples, dated between the 7th and the 6th century BC, belong to different sectors of the site. Their petrographic, mineralogical and geochemical characterization was performed by optical microscopy (OM), X-ray powder diffraction (XRPD), X-ray fluorescence (XRF), electron probe micro-analysis (EPMA), and Raman spectroscopy (RS). The compositional data obtained were also subjected to the principal component analysis (PCA) in order to highlight similarities and differences among the samples. By combining geochemical and petrographic data, we were able to identify several different fabrics. Furthermore, the study provided valuable information on the firing temperatures of some samples and the provenance of the raw materials, by analyzing the chemical composition of clinopyroxenes present as non-plastic inclusions. View Full-Tex

A petro-chemical study of ancient mortars from the archaeological site of Kyme (Turkey)

Fourteen samples of ancient mortars (joint mortars and plasters) from the archaeological site of Kyme (Turkey) were studied by optical microscopy (OM), X-ray fluorescence (XRF), X-ray powder diffraction (XRPD), scanning electron microscopy (SEM-EDS) and micro- Raman spectroscopy to obtain information about their composition.The study allowed us to identify a new type of plaster inside the archaeological site of Kyme, not detected by previous studies of this site, in which vegetable fibers were intentionally added to the mixture. The combination of a petrographic analysis on thin sections by polarized light microscopy with a chemical analysis, has allowed us to highlight similarities and differences between the mortars and to get information about the evolution of constructive techniques in the archaeological area

Physical mechanical consolidation and protection of Miocenic limestone used on Mediterranean historical monuments: the case study of Pietra Cantone (southern Sardinia, Italy)

The present work aims to study the consolidating and protective chemical treatments of the Pietra Cantone, a Miocenic (lower Tortonian) limestone widely used in important monuments and historical buildings of Cagliari (southern Sardinia, Italy). Similar limestones of the same geological period have also been used in several important monuments of Mediterranean area, i.e., Malta and Gozo Islands, Matera (central Basilicata, Italy), Lecce (southern Puglia, Italy) and Balearic Islands (Spain). The Pietra Cantone limestone shows problems of chemical–physical decay, due to their petrophysical and compositional char- acteristics: high porosity (on average 28–36 vol%), low cemented muddy-carbonate matrix, presence of phyllosil- icates and sindepositional sea salts (\3%). So, after placed in the monument, this stone is easily alterable by weath- ering chemical processes (e.g., carbonate dissolution and sulfation) and also by cyclic mechanisms of crystalliza- tion/solubilization of salts and hydration/dehydration of hygroscopic phases of the clay component. To define the mineralogical-petrographic features (composition, texture) of limestone, the clay and salt crystalline phases, the optical microscope in polarized light and diffraction anal- ysis were used. To define the petrophysical characteristics (i.e., shape and size distribution of porosity, surface area(SBET), matrix microstructures, rock composition) and interactions of chemical treatments with rock, SEM–EDS analysis and N2 porosimetry with BET and BJH methods were used. To evaluate the efficacy of Na/K-silicates, ethyl silicate consolidants and protective nano-molecular silane monomer water repellent, the mechanical strengths (uni- axial compressive strength, point load and flexural resis- tance), water/helium open porosity, water absorption and vapour permeability data determined before and after the chemical treatments of the Pietra Cantone samples from monument were compared

Mappatura delle pietre presenti nella facciata della chiesa di San Frediano (Pisa, Italia)

In questo articolo si riporta la mappatura dei materiali utilizzati nella facciata della chiesa di San Frediano (Pisa, Italia), che è stata inserita, insieme ad altri monumenti ed opere d’arte di eccezionale importanza (Palazzo Vecchio a Firenze, Cattedrale di Toledo, opere di Masaccio e Masolino) come cantiere di ricerca diagnostica nell’ambito del Progetto Europeo «RIS+ Toscana: Trasferimento di tecnologie innovative per i Beni Culturali». La distribuzione dei materiali impiegati indica che la facciata della chiesa di S. Frediano è stata realizzata principalmente con litotipi di provenienza locale, presenti comunemente negli edifici pisani di epoca medioevale. Essi provengono dalla costa tirrenica a sud di Livorno (calcareniti sabbiose, conosciute localmente con il nome di «Panchina»), dal Monte Pisano (quarziti, brecce calcaree e calcari neri) e dall’Isola d’Elba (monzogranito). Nella porzione inferiore della facciata, elementi ornati, stipiti e architravi dei portali d’ingresso sono realizzati con marmi bianchi di varia provenienza (marmo del M.te Pisano, marmi apuani e marmi del bacino Mediterraneo orientale)