Mining operations generate sediment erosion rates above those of natural landscapes, causing persistent contamination of floodplains. Riparian vegetation in mine-impacted river catchments plays a key role in the storage/remobilization of metal contaminants. Mercury (Hg) pollution from mining is a global environmental challenge. This study provides an integrative assessment of Hg storage in riparian trees and soils along the Paglia River (Italy) which drains the abandoned Monte Amiata Hg mining district, the 3rd former Hg producer worldwide, to characterize their role as potential secondary Hg source to the atmosphere in case of wildfire or upon anthropic utilization as biomass. In riparian trees and nearby soils Hg ranged between 0.7 and 59.9 μg/kg and 2.2 and 52.8 mg/kg respectively. In trees Hg concentrations were below 100 μg/kg, a recommended Hg limit for the quality of solid biofuels. Commercially, Hg contents in trees have little impact on the value of the locally harvested biomass and pose no risk to human health, although higher values (195-738 μg/kg) were occasionally found. In case of wildfire, up to 1.4*10^-3 kg Hg/ha could be released from trees and 27 kg Hg/ha from soil in the area, resulting in an environmentally significant Hg pollution source. Data constrained the contribution of riparian trees to the biogeochemical cycling of Hg highlighting their role in management and restoration plans of river catchments affected by not-remediable Hg contamination. In polluted river catchments worldwide riparian trees represent potential sustainable resources for the mitigation of dispersion of Hg in the ecosystem, considering i) their Hg storage capacity, ii) their potential to be used for local energy production (e.g. wood-chips) through the cultivation and harvesting of biomasses and, iii) their role in limiting soil erosion from riparian polluted riverbanks, probably representing the best pragmatic choice to minimize the transport of toxic elements to the sea.

Archaeological investigations of the Colline Metallifere district (Southern Tuscany, Italy) have highlighted several Medieval sites located close to the main Cu-Pb-Fe (Ag) ore occurrences. This study is focused on the investigation of late-medieval slags from Cugnano and Montieri sites using both geochemical and mineralogical methods to understand slag heterogeneities as result of ore differences and technological processes. Matte-rich slags present in both sites (with abundant matte ± speiss and frequent relict phases) represent waste products related to primary sulphide ore smelting to obtain a raw lead bullion. The distribution of slags between the Ca-rich or Fe-rich dominant composition, and the consequent mineralogy, are tracers of the different ore–gangue association that occurred in the two sites. Silver is present only in very small matte-rich slags and ores enclosed within the mortar of the Montieri site; wastes derived from silver-rich mineral charges were probably crushed for the recovery of silver. Matte-poor slags found at Montieri represent a second smelting; raw lead bullion obtained from matte slags (both Fe- and Ca-rich) was probably re-smelted, adding silica and Al₂O₃-phase-rich fluxes, under more oxidizing conditions to reduce metal impurities. This second step was probably employed for Zn-rich lead ores; this process helped to segregate zinc within slags and improve the quality of the metal.

An ultraportable hyperspectral camera operating in the Vis–NIR range (400–1000 nm) was used in this study for the non-invasive analysis of a selection of Italian maiolica wares and sherds from the Museo Nazionale del Bargello in Florence, Italy. The studied objects included authentic archaeological sherds, nineteenth-century forgeries, and ceramics of uncertain origin. The primary aim of this study was to evaluate the efficacy of hyperspectral imaging (HSI) spectroscopy combined with multivariate analysis for examining highly refractive and three-dimensional glazed ceramic artefacts within the constraints of a museum environment, including imperfect lighting conditions. Two data processing pipelines were tested: one based on principal component analysis (PCA) with score plots and the other on spectral angle mapper (SAM) classification obtained through the ENVI Spectral Hourglass Wizard (ENVI-SHW). The analyses enabled the discrimination between original parts and/or restored parts and additions. Among others, a complex assemblage of original sherds, restored parts, and non-ceramic parts was observed in a Renaissance pastiche vase. Furthermore, the method enabled the identification of the various chromophores providing clues on the artistic colour palette. In particular, the identification of chromium in the blue and green glazes of two objects of uncertain chronology suggested that they were not made before the nineteenth century. The acquisition of a larger and more detailed database of HSI data on maiolica glazes is strongly encouraged to improve the applicability of this method in authenticity, art-historical and archaeological studies.

The characterization of the layered structure is of paramount importance for the study of maiolica wares (tin-glazed pottery). This paper presents the potentialities of Terahertz Time-Domain Imaging (THz-TDI) as a tool to perform non-invasive stratigraphic analysis of the maiolica objects under test. Samples with different types of stratigraphy, as testified by preliminary SEM-EDS analysis, were investigated by THz-TDI in laboratory conditions. The collected THz data were processed by means of noise filtering procedures and a time-of-flight-based imaging approach and the achieved results corroborate the ability to identify glaze layers, whose electromagnetic properties, i.e., the refraction index and the dielectric permittivity value, were estimated by taking into account both THz-TDI and SEM-EDS data. However, layers applied over the white glaze (namely, a transparent overglaze and a luster decoration) were not detected, probably since their thickness is below the range resolution of the adopted THz-TDI system. Morphological features hidden under the surface were also identified and they provided information about the manufacturing technique.

The manufacturing of Italian maiolica (tin-glazed pottery) was extremely appreciated during the Middle Ages and Renaissance, leading to the production and collection of a rich cultural heritage. This pilot study aims to characterize the production technique and the origin of the lead used as a flux in a set of samples of maiolica glazes made in the area of Florence over a wide time span, ranging from the fifteenth to the nineteenth century. In particular, this is the first study that applies provenance analysis, using lead isotopes, to tin-glazed artefacts made in the site of Montelupo Fiorentino and by the Ginori manufactory in Doccia (Florence, Italy), both important production centres of ceramics in Italy. The samples were first analysed by scanning electron microscopy to characterize their layer structure and chemical composition. Lead isotope analysis was then performed by thermal ionization mass spectrometry and showed that the samples tend to be distributed into distinct groups according to their period of production. Moreover, the comparison with the lead isotope composition of the deposits of the European and circum-Mediterranean area from which lead was historically extracted showed that the isotopic composition of the samples differs from that of the Italian deposits, suggesting that lead was imported from abroad. The isotopic composition of all the investigated maiolica glazes is compatible with German ore deposits, in agreement with what is reported by the historical sources relating to the lead supply areas.