Colline Metallifere Research Articles

Mining under the canopy: Unveiling the archaeo-mining record in the Colline Metallifere with LiDAR analysis and multidisciplinary studies

The study of ancient disused mining contexts in the Mediterranean region is particularly challenging due to the impact of modern reclamation works and the presence of dense vegetation, which impede the application of conventional archaeological research methods.Pivoting on the multidisciplinary approach driven by the ERC nEU-Med project to the study of historical landscapes, and thanks to a new LiDAR survey promoted by the project in 2019, new investigations were carried out in ancient and modern mining contexts in the territory of Colline Metallifere (southern Tuscany, Italy). The district is renowned for its important metal deposits characterized by copper, lead, zinc and silver vein bodies that have been mined since the Bronze Age, with a particularly intense phase of exploitation during the Medieval period. The primary objective of the LiDAR DTM analysis was to map features and delineate the characteristics of the archaeo-mining landscape in five densely vegetated contexts. The analysis revealed numerous novel evidence related to mining activities (574 within the five territorial samples analyzed in this contribution), of which 72% were also inspected through fieldwalking surveys. These features have been interpreted by means of archaeological surveys, documentary research and statistical and spatial analysis. A particular focus was placed on the study of the most prevalent type of feature, which is the mining shaft. The development of reliable parameters of interpretation, including the dimensional aspects of each individual mining shaft (area, diameter and depth of the basin), the distances between shafts, and presence or absence of dumps, played a crucial role in disentangling the complex topography of the mining sites. The favourable results achieved through this study will enable the application of the method on a larger scale to other nearby mining contexts, overcoming the constraints of accessibility and visibility that have so far significantly influenced the analysis of mining territories.

Grouping Ceramic Variability with pXRF for Pottery Trade and Trends in Early Medieval Southern Tuscany. Preliminary Results from the Vetricella Case Study (Grosseto, Italy)

The characterization of archaeological ceramics according to their chemical composition provides essential information about the production and distribution of specific pottery wares. If a correlation between compositional patterns and local production centers is assumed, pottery manufacturing and trade and, more generally, economic, political, as well as cultural relations between communities and regions can be investigated. In the present paper, the combined application of portable XRF and statistical analysis to the investigation of a large repertory of ceramic fragments allowed us to group the assemblage by identifying geochemical clusters. The results from the chemical and statistical analysis were then compared with reference ceramic samples from the same area, as well as with macroscopic and petrographic observations to confirm, coalesce or sub-divide putative sub-divisions. The study of 141 samples from different sites located within a wide area spanning across the Colline Metallifere and the coast (Monterotondo Marittimo, Roccastrada, Donoratico, and Vetricella) provided new clues for a new interpretive archaeological framework that suggests that there was a well-defined organization of pottery manufacturing and circulation across southern Tuscany during the early medieval period.

Economic rebound versus imperial monopoly: Metal provenance of Early Medieval coins (9th–11th centuries) from some Italian and French mints

This paper represents the first systematic Pb isotope investigation of Italian Medieval coins and aims to provide new parameters for a general historical interpretation of coin production and circulation in Medieval Europe. We collected more than one hundred specimens, minted in a period between 9th − 14th centuries AD and coming mostly from archaeological sites of Tuscany. Here we report the results on the oldest group of (44) coins, dated between the end of the 9th and 11th centuries. All coins where previously characterized with handheld X-ray fluorescence (pXRF) analysis and lead isotope composition (PbIC) was performed using an MC-ICP-Mass Spectrometer. The Carolingian coins have PbIC compatible with Melle silver district; the few Carolingian coins possibly minted in Italy (Venice and Milan) are also compatible with ore districts such as Melle and Harz Mountains. Coins in the names of Italian rulers (9th-10th century) from Lucca, Pavia and other uncertain mints show PbIC compatible with Melle, Black Forest and the Harz Mountains as well. A quite similar pattern applies to coins in the names of Otto I-III and Conrad II (10th-11th century) from Lucca and Pavia mints, although they show a better overlap with the Harz Mountains. The vast majority of early medieval coins issued by the Italian mints investigated in the present paper show isotope compositions that do not match with silver (lead-copper) mines from the Colline Metallifere district of southern Tuscany, notwithstanding their exploitation in the considered period is suggested by many settlements located near mining sites.

Medieval Pb (Cu-Ag) Smelting in the Colline Metallifere District (Tuscany, Italy): Slag Heterogeneity as a Tracer of Ore Provenance and Technological Process

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.

Archaeometric Provenance Constraints for Early Medieval Sparse Glazed Pottery from Donoratico (Livorno, Italy)

The study of a huge repertory of sparse glazed ware from Donoratico (Livorno, Italy) dated back to the ninth century was carried out to investigate the production technology via petrographic, chemical, and isotopic investigations. The mineralogical and chemical evidence suggested the application of a lead oxide flux to an unfired non‐calcareous ceramic body, in accordance with late Antique and early‐Medieval traditions. The isotopic investigation of the glazes also suggested different sources for PbO, which was frequently applied as a mix of different metal batches. The Pb isotopic record identified the Southern Tuscany districts (Campiglia Marittima and Colline Metallifere) and a source controlled by the Carolingian kings in the northern districts of Central Europe (either in Aquitaine or in the Middle German ore districts) as the most reliable sources. SEM‐EDS showed the presence of tin impurities in the form of secondary cassiterite agglomerates in most of the glazes obtained by the use of local lead. The presence of cassiterite veins in Southern Tuscany lead sulphide deposits was considered as the main cause for tin impurities in the glazing mixture and, thus, an important marker for the exploitation of local lead.

The conversion into high forest of Turkey oak coppice stands: methods, silviculture and perspectives

The goal of this study is to assess the impact of different thinning approaches for coppice conversion into high forest of Turkey oak stands in Italy. The stand structure and the tree/shrub diversity were analyzed in 27 long-term monitoring plots from 7 experimental trials in the Colline Metallifere district (Tuscany, Central Italy) to verify the consistency of the original cultivation goals with the current stand structures. Three different approaches were applied from 1969 onwards: thinning from below, selective thinning, and no-management. Three indexes of specific diversity (Specific Richness, Shannon index and Importance Value) and two indexes of vertical diversity (Vertical Evenness and Coefficient of variation of tree height) were used to analyze and compare the outcome of management practices. The results showed a significantly higher dimensional variability and basal area, and a more complex vertical diversity in control plots and in the plots subject to selective thinning, as compared with plots subject to thinning from below. Tree species richness was high in all plots, independently of the thinning type applied. Based on our results, we suggest Turkey oak-dominated transitory stands to be initially managed by thinning from below, which is easy to be implemented and economically feasible. Selective thinning may be applied later with the aim of promoting sporadic but valuable tree species and increasing tree species diversity.

The acidic waters in Italy: a brief overview

The present study is aimed at providing a brief overview of the Italian acidic waters based on literature and unpublished data. Acidic waters in Italy, as elsewhere, are relatively common and associated with extremely variable geological settings. Owing to their peculiar features, these waters may seriously affect the environment and the ecosystems. Along the Apennine belt, the western and inner sectors of the Italian peninsula record an anomalous geothermal gradient, mostly overlapping with the Neogene-to-present magmatism, that explains the presence of a huge amount of CO2(H2S)-rich gas and thermal water discharges, geothermal fields (e.g. Larderello and Mt. Amiata) and ore deposits (e.g. Fe- and polymetallic sulfides, e.g. Elba Island and Colline Metallifere). Acidic waters (pH ≤5) from volcanic and geothermal areas show outlet temperatures and Total Dissolved Solids (TDS) from 10 to 96°C and <1 to ≈30 g/L, respectively, with a chemical composition usually belonging to the Ca-SO4, NH4-SO4 or Na-Cl facies. Frequently, they are related to bubbling and boiling pools due to the interaction between deepsourced gases and shallow aquifers or meteoric waters. Concentrations of heavy metals and metalloids are in most cases high. Extremely high contents of metals are also recorded for those acidic waters that characterize the main Italian mining districts, mostly located in Sardinia (not included in the present study), Tuscany and NW Alps, where they are related to Acid Mine Drainage l.s. or Acid Rock Drainage. The pH values are as low as 2.08, with variable TDS concentrations. Compositionally, they are Na-SO4, Ca(Mg)-SO4, and/or Mg(Ca)-SO4 waters, prevalently due to oxidative processes affecting polymetallic sulfides.

Geochemistry of groundwater in a sector of the Colline Metallifere mining district (Tuscany, Italy)

This paper reports the results of a geochemical study of groundwater in the Montioni area, a sector of the Colline Metallifere mining district (Tuscany, Italy). The aim of the study was to distinguish the hydrochemical facies of groundwater, to define their origin and flow systems, and to identify the main geochemical processes ruling their chemical composition. The physico-chemical parameters (temperature, pH, electrical conductivity and redox potential) and concentrations of major ions (Na, K, Ca, Mg, Cl, HCO3 and SO4) measured in 203 groundwater samples collected in the period 1996-2014 from four springs and three piezometers, were used for this study. The analytical data suggests that the Montioni area is characterized by a complex hydrogeological system consisting of three main groundwater types: (1) Ca-SO4 waters of the deep regional aquifer system hosted by Triassic carbonate-evaporite formations, rising through fractures and faults; (2) Ca(Na)-HCO3 and Na-HCO3(Cl) waters fed by recent meteoric recharge and characterized by shallow circulation within calcareous-siliceous and clayey-calcareous-arenaceous formations of the Tuscan Nappe, respectively; (3) Ca-SO4-HCO3 waters arising by mixing of deep Ca-SO4 fluids and shallow Ca(Na)-HCO3 groundwater. The main processes determining the geochemical features of groundwater in the study area are: (1) carbonate dissolution (mainly calcite) in the surface recharge zone, as well as sulphate (gypsum and anhydrite) and carbonate (calcite and dolomite) dissolution in the deep aquifer hosted by Triassic carbonate-evaporite lithologies; (2) ion exchange reactions occurring in the surface water circulation system within clayey rocks of the Tuscan Nappe (Scaglia Toscana Group); (3) mixing of deep and shallow groundwater.

The evolution and political use of élite domestic architecture at Poggio Civitate (Murlo)

The hill of Poggio Civitate is located immediately adjacent to the small mediaeval town of Murlo, c.25 km south of Siena (fig. 1). Situated at the juncture of Tuscany's mineralrich Colline metallifere and the agricultural abundance of the Crete senese, Poggio Civitate's inhabitants drew upon the area's vast resources to emerge as a regional center of power in the 8th through 6th c. B.C.Excavation in 2015 at the Etruscan site revealed a previously undocumented phase of monumental domestic architecture. The building in question lies immediately west of the Piano del Tesoro plateau, in the modern property zone known as Civitate A. Its architectural form, as well as the materials recovered both upon and beneath its floor, suggest that it dates earlier than the architectural complex known on the adjacent plateau.

A spatial model for sporadic tree species distribution in support of tree oriented silviculture

This technical note describes how a spatial model for sporadic tree species distribution in the territory of the Unione di Comuni Montana Colline Metallifere (UCMCM) was built using the Random Forest (RF) algorithm and 48 predictors, including reflectance values from ground cover - provided by satellite sensors - and ecological factors. The P.Pro.SPO.T. project - Policy and Protection of Sporadic tree species in Tuscany forest (LIFE 09 ENV/IT/000087) is currently carried out in this area with the purpose of initiating the implementation of tree oriented silviculture in the Tuscany forests. Tree oriented silviculture aims at obtaining both forest biodiversity protection and local production of valuable timber. After creating a map showing the probability of presence of sporadic tree species, it was possible to identify the most suitable areas for sporadic tree species which are under protection according to the regulation of the Tuscany Region.Using data and software provided free of charge, and applying the RF algorithm, distribution models could be developed in order to identify the most suitable areas for the application of tree oriented silviculture. This can provide a support to forestry planning that includes tree oriented silviculture, thus reducing its implementation cost.

A STELLAR REPRESENTATION IN THE PALEOLITHIC

In the early 70's, an extended archaeological campaign was carried out in Maremma, Tuscany, by researchers of the University of Florence. There, to the south of the Colline Metallifere, it lies a vast region, which is very rich in prehistoric remains and extends as far as the Tyrrhenian coast, westward, and Grosseto city, southward. Most archaeological finds date back to Iron Age, some thousand years b. C., and are due to the Villanovan culture and to the Etrurian civilization. The names of some among such sites are very well known, like Baratti, Vetulonia or Roselle. In the present case, the place of interest is almost unknown and it is situated in a country fea- tured by Karst formations. At the mentioned time, one of the authors (FM), as a member of archaeological team, was exploring the territory around a spot called Vado all’Arancio and discovered a natural cavity which turned out to have been inhabited in prehistoric times. Luckily, the small cave has remained sealed until then because of a landslide and therefore a large stone was, and still is, almost completely blocking the entrance. The survey work could be performed only by slithering along the ground. The following excavations conducted by FM revealed very interesting findings. First of all, there were two human burials, one adult male and one child, with the skeleton well preserved and almost complete. The graves were at different depths, not far below ground level, however. It is important to stress this aspect, because the skeletons were still composed and therefore, very probably, there had been no intrusions in the inner part of the cave ever since. Moreover they were also found various worked items, mainly stone tools and several animal bones dressed with wildlife engravings. Among these are the typical depictions of symbolic male and female, namely horse and bison, respectively. It is believed that all the worked stuff in the cave was intended to represent something observed in nature.

PROBLEMS AND PROSPECTS OF THE CHESTNUT TIMBER CHAIN IN TUSCANY

The chestnut timber chain in Tuscany is divided into two main production lines: posts and industrial timber. In the first case, regional manufacturing of raw material mostly covers the domestic needs. As for industrial uses, in spite of the high demand for quality timber, the scarce development and quality of production also affects the manufacturing stages. The main reason lies in the everlasting difficulty of supplying chestnut timber assortments for industrial purposes. The production is extremely inadequate, especially in terms of quality. The Italian raw material can be only partially qualified as industrial timber, because of the lack of suitable size and quality requirements. Accordingly, industrial timber is increasingly being imported from foreign markets. The aim of this paper is to assess whether the growth of local supply can be sustained by first-phase processing enterprises in terms of quality timber assortments. The survey analyzed the structure of several enterprises located on Monte Amiata (SI) and the Colline Metallifere (GR). Data necessary for gaining more knowledge about the first step in the timber-forest chain were acquired from questionnaires submitted to the owners of the firms operating in this sector. The information acquired included firm size, source of woody material, availability and annual quantity of wood sales, prices of assortments, and machinery and equipment owned by each firm. The interviews shed light on several aspects such as the interest in local woody material supply in spite of difficulties in sourcing the same. The sample consisted of small-sized enterprises, family-run entities, poorly equipped for machinery, mainly represented by posts marketed in the local area. As for the goal of this survey, it must be pointed out that the majority of firms processing chestnut timber are located on Monte Amiata, where chestnut stands are one of the main forest types; while in the Colline Metallifere, these firms focus more on oak species since chestnut plays a marginal role and no timber trading activity exists among the firms found in the two surveyed areas.

GENETIC CHARACTERIZATION OF TUSCAN CHESTNUT GERMPLASM: GENETIC AND GENOTYPIC VARIATION AMONG POPULATIONS OF THREE DIFFERENT AREAS

The study was conducted to characterize 131 chestnut plants collected in three different areals of the Tuscany region (Garfagnana, Colline Metallifere, Amiata). The three areals are well separated without continuous chestnut presence. Molecular analysis was performed with 8 microsatellite markers. The 131 plants belonged to 39 names, only 1 of which was present in all the tree population while 4 were present in two population. The results of the fingerprinting showed that identical genotypes were present only within each population. The final number of genotypes was set to 102, once eliminated homonyms and synonyms. The three presented populations differed at the genetic level, although the plants of Colline Metallifere and Amiata shared some alleles. At the genotypic level the three populations differed statistically. Hence, the populations presented different genetic pools and may represent independent sources of variation in breeding. For one of the loci a high level of homozygosity was found in all the populations suggesting a possible correlation between this marker and a gene selective against heterozygosis.

Colline Metallifere (Tuscany, Italy)

Since the 1980s, in Italy, and Tuscany in particular, considerable experience has been developed in research on the mining landscape in relation to the geography of population, with particular attention to the Medieval period. Numerous research projects carried out in the Colline Metallifere areas of Livourne and Grosseto by the Archaeology Department of the University of Sienna (Prof. Riccardo Francovich) have revealed the huge potential offered by this territory for the study of the population, extraction and production dynamics of the pre-industrial period as well as the necessity for rigorous surveillance of the remains of these activities which have been progressively eroded by recent and massive extraction activities and by the current development of housing and infrastructure. In the Livourne Colline Metallifere area, we have already advanced from the research phase to the creation of a fully operational Archaeo-mining Park which has made it possible to protect an extensive territory containing a wealth of pre-industrial and industrial archaeological evidence, including the mining village of Rocca San Silvestro. In the Grosseto province, the Colline Metallifere grossetane Technological and Archaeological Park was recently created. The aim of this institution is to preserve and enhance historical and archaeological heritage of prime importance which twenty years of research have contributed to uncover across a vast territory.

The tectono-metamorphic record of the Tuscan Nappe from the Colline Metallifere region (Northern Apennines, Italy)

This paper deals with a structural and petrographic study carried out on key outcrops belonging to the Tuscan Nappe exposed in the Colline Metallifere region (Montieri-Poggio Prugnoli). Here, the Tuscan Nappe was affected by polyphase deformation characterised by superposed folding events (F1, F2 and F3) and related tectonic foliations (S1 and S2) in agreement with the structural setting described for the Tuscan Nappe exposed both in other places of southern Tuscany, and in the Alpi Apuane region. The development of F1 folds was accompanied by metamorphism which produced a sin-kinematic mineralogical assemblage developed on the S1 tectonic foliation. This paragenesis, consisting of calcite + quartz ± muscovite ± Fe- and Ti-oxides, is indicative for a temperature of about 200-300°C according to the T values estimated for the F1 folding event documented for the Tuscan Nappe of the Apuan Alps, suggesting a very low grade metamorphism which affected the Tuscan Nappe during its stacking in the Northern Apennines collisional belt

Enhancing chestnut coppices: silvicultural management and socio-economic context.

Castanea sativa is one of the most important species for timber production in Italy but, both management system, ownership type and wood chain structure, aren’t able to enhance enough the market value of wood assortments. Although the high demand of quality timber, the internal production is heavily reduced, mainly as far as timber quality is concerned and because of the lack of suitable timber sizes. In this context, experimental trials have been approached to identify and verify which silvicultural methods are best suited to reach high yields depending to the investments needed and the local socio-economical condition. Two technical approaches were evaluated: stand silviculture and single-tree oriented silviculture. As for the socio-economical aspects, a few demographic indexes have been examined and the first-phase processing enterprises acting in the concerned area were analyzed. The goals of this paper are to evaluate the biological response to the applied silviculture, to analyze the problems arisen and to estimate the applicability of the proposed methods in relation to the different socio-economic contexts. The research has been carried out in Tuscany in two important forest areas - Monte Amiata and Colline Metallifere - in young chestnut coppices characterized by an homogeneous stand density and a good site index. The two examined districts showed some similarities but they have mainly highlighted important differences about the social structure and concerns and enterprises characteristics. The area of Monte Amiata is typified by a higher residents density then the Colline Metallifere but only 1/3 of the population is employed in the agro-forest sector. In addition, in the Monte Amiata district most concerns are sized less than 2 hectares and chestnut is the main forest species. On the contrary, in the Colline Metallifere the agro-forest sector (57% of workers) is one of the main sources of income for the local communities and medium-sized concerns are noteworthy present. Chestnut stands have here a marginal role, oaks are dominant and the prevailing assortment is firewood. From a silvicultural viewpoint, both the studied areas showed a quite good potentiality, suitable st1\:*{behavior:url(#ieooui) } /* Style Definitions */ table.MsoNormalTable {mso-style-name:Tabella normale; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-parent:; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:Times New Roman; mso-ansi-language:#0400; mso-fareast-language:#0400; mso-bidi-language:#0400;}

New data on the paleogeography of Southern Tuscany (Italy) since Late Miocene time

In order to add new data to the knowledge of the paleogeography of Southern Tuscany and the Tuscan shelf, a multidisciplinary study on the petrology and distribution of magmatic clasts of the widely exposed Messinian, Pliocene, and Quaternary sediments in Southern Tuscany was carried out. The magmatic clasts consist of porphyric aplites and subordinate granite porphyries, which derive from eroded subvolcanic acidic bodies. The porphyric aplite clasts were analyzed in detail to define their textural, petrographic, and chemical (major and trace elements, Sr and Nd isotopic composition) features. The porphyric aplite clasts show strong affinities with the 8.4–7.9 Ma old Capo Bianco aplite, whereas the granite porphyry clasts have affinities with the Portoferraio porphyry (ca. 8 Ma) which intruded the Cretaceous and Paleogene Flysch Units and the Ophiolitic Unit in central-western Elba Island (Northern Tyrrhenian Sea). The present outcrops of the Capo Bianco aplite in central Elba Island cannot be considered as the source rock for the Late Messinian gravels, because at that time such Capo Bianco aplite (located at the lower portion of the laccolitic stack) was there buried at several kilometers depth. However, other Capo Bianco-like aplitic bodies outcropped during the latest Miocene in the host rocks above and also around the 6.8 Ma M. Capanne Pluton in the western Elba areas. The exposure of such bodies was made possible by the activation of the central Elba detachment fault (=CEF), due to the uplift of the M. Capanne pluton. This uplift displaced a significant portion of the cover (including the upper portion of the laccolithic stack) of the granitoid body at about 6, 7 Ma, thus allowing the erosion of the lower part of the laccolith complex made up of the Capo Bianco aplite and of the Portoferraio porphyry and leaving still buried the M. Capanne pluton. The paleogeographic picture of Southern Tuscany arising from the collected evidences is the following: during Late Messinian, the clasts were dispersed by a SSW/NNE-trending complex fluvial system in the Colline Metallifere area. The Early Pliocene extensional tectonics cut off the detrital inputs from the Messinian source areas, because of the onset of the Piombino Channel and of the Campiglia–Gavorrano Ridge. During the Pliocene, the clasts were cannibalized from the previous sedimentary units and reached the easternmost areas due the eastward progressive uplift of the Colline Metallifere, likely connected with the coeval magmatic intrusions. Finally, the Quaternary regional uplift allowed a drainage reversal and a backward displacement of the aplitic clasts toward the Tyrrhenian coast. These data point to a rapidly evolving drainage pattern in Southern Tuscany during the considered time interval, which was mostly driven by the intrusion and uplift of the Messinian to Quaternary plutons. The morpho-tectonic evolution is well framed also within the models since long accepted for the Northern Apennine geodynamics, characterized by an overall eastward shift of the orogenic front.

Metallurgy, environmental pollution and the decline of Etruscan civilisation

The Etruscans were justifiably famous in antiquity for their advanced metallurgy and for the rich mineral resources of their region (including La Tolfa, the Colline Metallifere, Mont'Amiata and Elba). We offer a new perspective on certain Iron Age and Archaic (ca. 1,000-480 BC: ) Etruscan industrial and habitation sites, and on the problem of heavy metal poisoning, still being investigated today, coincidentally in some of the same areas that originally saw Etruscan mines and workshops. This study investigates ancient sources, including literature and excavation reports, in the light of modern studies of heavy metal poisoning on human beings, plant and animal life. Furthermore, it is the first to use non-invasive Niton X-ray fluorescence analysis of samples of Etruscan (strictly ethnically Faliscan) hair (c. 350 BCE: ). The findings show the strong likelihood of heavy metal poisoning in areas of Etruscan metallurgical activity with the effects of this being responsible for or contributing to the abandonment of a number of these sites around the 6th century BC: . No thoroughly satisfactory explanation of this phenomenon has previously been offered. However, findings suggest that Faliscan women, represented by sample CG 2004-6-2, were not exposed to high levels of arsenic in life, which is not perhaps surprising for an urban aristocratic woman of the mid-4th century BC: . The reasons for the abandonment of several flourishing settlements are without doubt complex, and include political and social change. We suggest heavy metal contamination as an additional stimulus to the noted phenomenon of the peaceful abandonment, at the beginning, and at the end of the 6th century BC: , of sites in southern and northern Etruria such as Marsiliana d'Albegna (late 7th c.), Lago dell'Accesa, Acquarossa and Poggio Civitate-Murlo (late 6th c.). While the historical truth of the demise of Etruscan civilisation is much more complex, an interim set of related events, the desertion of several important settlements during and at the end of the Archaic period, might actually have been stimulated by the consequences of industrial pollution and arsenic poisoning. We call for archaeologists and curators to test any available human and animal remains in their museums and collections for evidence of heavy metal poisoning, taking due caution and consideration of course to the relevance of the aristocracy, and urge the application of analytical techniques developed in response to this serious modern problem, to provide additional insights into the ancient situation.

Impact of ancient metal smelting on arsenic pollution in the Pecora River Valley, Southern Tuscany, Italy

A significant As anomaly has been reported in the literature for stream sediments and unlithified Quaternary deposits of the Pecora River valley in Southern Tuscany, extending from the “Colline Metallifere” pyrite-base metals district to the Tyrrhenian Sea. The As anomaly spreads over several square kilometers around a core that exceeds 500 ppm. Several source contributions (from natural to anthropogenic) have been invoked to explain the observed As distribution in the Pecora Valley, including the metal-working industry which was active in this area, particularly in Etrusco-Roman times and in the Middle Ages. In order to evaluate the contribution of ancient mining and metallurgical activities in the Pecora Valley to elevated As concentrations in the environment, a detailed mineralogical and geochemical survey of metallurgical slags and smelted ore minerals was undertaken from six different sites through the Pecora Valley: Poggio Butelli (Etrusco-Roman iron slags); Sata Creek, Arialla, Marsiliana, Forra and Cascata sites (all Medieval base metals slags). The As content of Etrusco-Roman slags is relatively low (few tens of ppm), whereas Medieval slags show variable, but higher amounts of base metals (±Ag) (ranging from tens to tens of thousands ppm) and As (up to 267 ppm, with average contents of about 40 ppm). Arsenic is mostly partitioned in sulfides disseminated through the glassy groundmass rather than in solid solution with the glassy matrix. Remnants of the ore used for base metal and Ag smelting during the Middle Ages had the highest As contents (up to about 1000 ppm). The overall As concentration in the slags, independent of age and type, is generally lower than that found in stream sediments and Quaternary alluvial deposit outcrops of the upper Pecora Valley. Textural observations indicate that exogenous alteration of slags is minor and mostly confined to superficial exposures of matte droplets or along fractures; metal particles embedded within the glassy groundmass, even those located a few micrometres from the surface, appear to be unaltered. It is suggested, therefore, that As and contaminant metal contributions to the Pecora valley by archaeometallurgical slags was minor, at least for slags from the last 2500 to 700 a BP. Similarly, based on gross mass balance calculations, airborne release of As due to smelting/roasting operations in the past cannot account for the observed extent of the As anomaly in stream sediments and Quaternary deposits. Although residues of unsmelted (or partially smelted) Fe–Cu–Pb–Zn charges or fluxes for base metal metallurgy contain much greater amounts of As than smelting slags, their relatively low abundance would limit the overall input of As into the Pecora river valley. On the other hand, concurrent research seems to indicate a major “geogenic” contribution to the As anomaly in the Pecora Valley.

Vegetation history, climate and human impact over the last 15,000 years at Lago dell’Accesa (Tuscany, Central Italy)

Interdisciplinary studies of the sediments of Lago dell’Accesa started in 2001. We present here results from the palynological study. The pollen diagram provides a record of vegetation and climatic change spanning over 15,000 years. The oldest pollen spectra show a late-glacial steppe vegetation typical of central and southern Italy during this period. The Late-glacial Interstadial, interrupted by two cooling events, is dominated by open deciduous oak forests. The Younger Dryas is represented by 150 cm of sediment and shows the presence of steppic vegetation. The Holocene vegetation is characterised by alternating dominance of deciduous oaks and Quercus ilex. The three zones characterised by Q. ilex are accompanied by peat layers marking lake-level lowering at ca. 8600–7900, 4600–4300 and 3700–2800 cal b.p. Between approximately 9000 and 6000 cal b.p. extensive Abies-forests existed on the Colline Metallifere located 15–20 km to the north and northeast of the lake. Local fir populations may also have existed by the lake. Human impact starts at approximately 8000 cal b.p. during the Neolithic period, and increases at ca. 4300 cal b.p.Castanea and Juglans pollen is recorded from ca. 2800 cal b.p. The impact of the Etruscan settlement near the lakeshore is shown in the increasing values of arable crops, species of secondary forest canopy (Ericaceae, Pinus, Pistacia, Myrtus) and anthropogenic indicators (Chenopodiaceae, Plantago lanceolata, Rumex etc).