Dissertations / Theses on the topic 'Archaeometry'

Advances in mass spectrometry in the second half of this century allowed very accurate measurements of isotopic compositions of various elements. In turn it was discovered that due to the radiogenic origin of some of these isotopes their composition often reflects the geochemical history of minerals and rocks. Terrestrial lead is composed of four isotopes, of which three are radiogenic in origin as daughters of uranium and thorium. In geochronology the isotopic composition of minerals helps in dating the ore and rock formations. However, if there is enough diversity amongst the isotopic compositions of different deposits, then their lead isotope composition can be used as a simple and unique 'fingerprint', which can be scientifically measured. This feature can be used as a powerful tool in the identification of sources of ancient metals, because it passes unchanged through the smelting and refining processes. However, one of the most important requirements for such 'lead isotope provenance studies' is empirical investigation of the 'fingerprints' of ore deposits which are relevant to a given archaeological research. In this dissertation the scientific foundations of lead isotope provenance studies are described and examined in detail. All available evidence concerning the possibility of distinguishing isotopically between different European ore deposits is examined and methods of visual and numerical evaluation of the lead isotope data are suggested. Two examples of applications to specific archaeological problems are also given: the identification of sources of metals used for production of Bronze Age Cretan weapons and of non-ferrous metals in the Roman Period in Southern Poland. The interpretation of lead isotope data for archaeological objects is based on nearly 1500 isotopic analyses of ores.

Abstract: In archaeological sites, there are many metals found in different conditions and different levels of damage. The metal artifacts are generally covered by oxide-based corrosion layers. Copper-based artifacts, including bronze products, can be found in a major part of cultural heritage sites, being extremely important to be conserved, as well as in need of careful cleaning procedures and effective means of oxidation protection. Accordingly, the aim of this work is to develop new chemical methods for the corrosion removal by using a green and environmentally friendly gel that enables both area and material selective cleaning, depending on the additives. Hydrogels are known to be very promising materials for corrosion removal, as they enable cleaning of the parts that are not easily reached or that cannot sustain liquids and can also keep cleaning solvents in the desired area and depth, i.e., high area selectivity. In addition, hydrogels are affordable, friendly and safe for the environment and for the conservators. The development of the hydrogels has been carried out in the following steps: 1) analysis of the copper surface in terms of hydrophilicity by means of contact angle measurement; 2) selection of the suitable polymer structure that has high wettability and compatibility with copper, such as poly(vinyl alcohol) (PVA) and sodium carboxymethyl cellulose (CMC), and preparation of their aqueous gel having a polymer concentration of 15% (w/w); 3) formation of hydrogel containing 7wt% citric acid as cleaning agent on electrochemically corroded copper surfaces. The cleaning efficiency and mechanism were evaluated using X-ray Diffraction (XRD) analysis and Infrared Spectroscopy (IR). Throughout these analyses, the desired gel formulation was obtained, which was then tested using chemically corroded coins to confirm the applicability of the gel for the cleaning of different objects.

This thesis presents a material-centered characterization of 120 geologic samples from four fine-grained basalt quarries on the Samoan Island of Tutuila. Previous unsuccessful attempts at definitive Tutuilan quarry differentiation have utilized x-ray fluorescence (XRF). In this study, clear differentiation of each analyzed quarry was achieved using instrumental neutron activation analysis (INAA). Biplots of canonical discriminant function scores for the INAA data illustrate clear separation based on the variation in chemical composition between each quarry. The samples analyzed not only define quarry separation, but also provide the "core group" for a preliminary baseline necessary for future artifact-centered provenance studies. Inclusion of these "core group" samples in the baseline was confirmed by stepwise discriminant analysis. These findings suggest the ability to determine quarry of origin on the island of Tutuila, which can elucidate the importance of individual Tutuilan quarries in the export and exchange of fine-grained basalts.

Thesis (Ph. D.) University of Missouri-Columbia, 2006.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on August 7, 2007) Includes bibliographical references.

This research aims to look at dietary practices of separate populations from across the Adriatic Sea (Italy and Croatia). Paleodietary studies through stable isotope analysis is a means to look at possible food catchments chosen by past communities in order to make educated assumptions of economic and cultural practices. Stable carbon and nitrogen isotope analysis was carried out successfully on 22 humans and 28 animal bones from four separate Bronze Age sites. The sites analyzed are Coppa Nevigata (Apulia, Italy), Gusica Gomila, Jukica Gomila, and Brnjica (Dalmatia, Croatia), all dated to the Bronze Age (approximately XVIII-XII century BCE). The main objective is to investigate the contribution of different food sources (terrestrial and marine) and to observe distinctions on animal versus plant proteins in the diet to examine dietary differences within each site. This will allow for a greater understanding of dietary patterns in both Bronze Age Italy and Croatia and to possibly investigate any differences between the two areas. Collectively, the sites have presented carbon and nitrogen isotopic ranges that illustrate a diet dominated with C3 terrestrial plants and relative consumption of herbivore animal proteins. Compared to recent studies of Bronze Age Italy and Croatia, the results correlate well with a diet consisting mostly of cultivated C3 plants. Although, the Bronze Age is an important period for the introduction for a new crop, the C4 plant group of millets, only two individuals from Brnjica show signs of small consumption of C4 plants and/or marine foodstuffs. The individuals from Coppa Nevigata do not indicate any C4 plant consumption which supports recent studies that millet has only been proven to be consumed in North and Central Italy during the Middle to Late Bronze Age. Two individuals from Coppa Nevigata do however indicate small consumption (15-20%) of freshwater foodstuffs. No significant differences in stable isotope values in terms of intrapopulation variations such as sex, age, burial type, or period as far as the samples have provided. This study contributes to our understanding of dietary practices in prehistoric Italy and Croatia and provides new data on Southern and Eastern regions of the Italian Peninsula, all of which are generally under-represented in the Bronze Age. Further it adds interesting information on a clear distinction between Northern and Southern regions of Italy, which suggests that food practices are a good means to investigate on past cultural complexity

Abstract: Selection and refinement of a method for copper corrosion removal were undertaken in an environmentally friendly way by using deep eutectic solvents (DES) integrated in a cellulose-based membrane. DES is a potential “green” solvent based on natural compounds. In this thesis, a DES composed of choline chloride and ascorbic acid in a 2:1 ratio, was prepared and used for copper corrosion cleaning. The DES was diluted with water and the DES to water ratio was optimized in terms of efficiency, time consumption, and selectivity of cleaning. It was found that DES solutions, having a concentration higher than 70 wt.% were suitable for dissolving copper corrosion products. Meanwhile, they exhibited a supressed dissolution ability of CaCO3 which is a common compound in many of the supporting structures used for copper artefacts. These solutions were then used for swelling cellulose membranes, and the swelling capacity was monitored for a week. The swollen membrane was put on an electrochemically corroded copper sheet for 24 hours. By removing the membrane, the green malachite layer was successfully removed from the copper sheet while preserving a reddish-brown cuprite layer. This was confirmed by performing X-ray diffraction analysis before and after cleaning the copper sample. For heritage objects, the defacing copper corrosion products of Cu (II) need to be removed apart from protective layer of cuprite. We concluded that the cellulose membranes containing DES solutions are promising materials for this purpose.

ABSTRACT: The aim of this thesis was to perform an archaeometric study of the collection of glass fragments, found during excavation of layers dated 6th-7th century AD of a room XII, 1 of the Horrea Vespasians, a complex of warehouses during the Imperial period on the Palatine Hill. These glass fragments were excavated only in 2017 and this is the first study that involves them. A non-destructive approach to study elemental composition of the fragments was chosen. A characterization of the glass fragments was performed by XRF and LA-ICP-MS. In this study, an attempt to reconstruct the production process with possible raw materials and colorants used was made. The results obtained in this study will contribute to the literature on Roman glass production,

The Euganean Hills (Veneto, NE Italy) are the most important quarry district in Italy for the extraction of trachyte, which has been carried out in tens of quarries all through the centuries, from Pre-Protohistory and, more intensely, from the Roman age onwards. Trachyte of the Euganean Hills has an age-old tradition of usage as carving and building stone, mainly in northern and central Italy, e.g., for manufacturing diverse everyday items and funerary and votive artifacts, as well as for building infrastructure, monuments, and in public and private construction. An archaeometric study of Euganean trachyte is here presented following two main research directions. The first involves the identification of criteria for recognizing provenance quarry of trachyte used in archaeological and historical materials, supported by a petrographic and geochemical database obtained from samples collected in the entire area of the Euganean Hills. The petrographic provenance tracers involve mineralogical composition and textural features of phenocrysts and groundmass, whereas the geochemical tracers comprise major- and trace-element composition of bulk rock and phenocrysts, in particular of mafic minerals. Trachyte provenance can be most precisely determined by applying multivariate relations based on phenocryst chemistry, which can be analyzed even on small, altered archaeological samples. The provenance markers were tested in a provenance study of Euganean trachyte used in Roman public infrastructure in Veneto, including roads, bridges and forum squares. The results provide insights into the commercial, political and economic dimension of the management of trachyte quarries and development of extraction activities in the Roman times, as well as into ancient trades in northern Italy and the main routes of stone circulation. The second research topic addresses the investigation of weathering and durability of Euganean trachyte used as building stone. Weathering crusts and patinas were detected on trachyte in urban environment, and their mineralogical and microstructural characteristics, major- and trace-element chemical composition were analyzed. The alteration products, mainly involving surface enrichment in carbonates, heavy metals, and carbon, represent an informative indicator of environmental conditions, in particular air quality, and chemical stability of the rock-forming minerals of trachyte and neighboring jointing mortars. Trachyte durability was also examined by a petrophysical and mechanical characterization of quarry samples, providing elements for aiding quality assessment by conservators-restorers and building companies. Particular emphasis is placed on the properties related to absorption, transport, and retention of water and aqueous solutions, in liquid and vapor state. Depending on porosimetric characteristics, i.e., pore volume, size, size distribution, shape, and degree of interconnection, different trachyte varieties exhibit a relatively wide array of technical performances, diversely affecting their decay behavior.
I Colli Euganei (Veneto) rappresentano il più importante distretto di cava in Italia per l’estrazione di rocce trachitiche, attività storicamente condotta in decine di cave e iniziata già in epoca pre-protostorica, poi intensificatasi a partire dall’età romana. L’importanza della trachite dei Colli Euganei nel patrimonio culturale, soprattutto del nord e centro Italia, si collega ad una tradizione millenaria di impiego nella manifattura di utensili e manufatti votivi e funerari, nella costruzione di infrastrutture e monumenti e nell’edilizia pubblica e privata. In questa tesi, si presentano i risultati di uno studio archeometrico della trachite euganea incanalato in due linee di ricerca principali. La prima riguarda l’identificazione di criteri per riconoscere la cava di provenienza della trachite usata in materiali di interesse archeologico e storico, supportata da un database petrografico e geochimico costruito su campioni prelevati nell’intero territorio dei Colli Euganei. I traccianti petrografici di provenienza comprendono la composizione mineralogica e le caratteristiche tessiturali dei fenocristalli e della matrice, mentre i traccianti geochimici considerano la composizione degli elementi maggiori e in traccia della roccia totale e dei fenocristalli, in particolare dei minerali femici. La maggior precisione nella determinazione della provenienza si ottiene applicando relazioni multivariate basate sulla composizione chimica dei fenocristalli, che può essere analizzata anche su campioni archeologici, spesso di dimensioni limitate e alterati. L’efficacia di questi indicatori è stata poi verificata in uno studio di provenienza della trachite euganea impiegata in Veneto in infrastrutture pubbliche di età romana, quali strade basolate, ponti e piazze forensi. I risultati di tale studio restituiscono un’idea della dimensione commerciale, politica ed economica in cui si inseriva la gestione delle cave romane e l’evoluzione delle attività estrattive, oltre a fornire informazioni sui traffici commerciali antichi sviluppatisi nel nord Italia. La seconda tematica di ricerca è impostata sullo studio del degrado e della durevolezza della trachite euganea usata come pietra da costruzione. Inizialmente, si sono individuate croste e patine di alterazione della trachite in ambiente urbano e se ne sono analizzate le caratteristiche mineralogiche e strutturali e la composizione chimica degli elementi maggiori e in traccia. I prodotti di alterazione, che si rilevano spesso come arricchimenti superficiali in carbonati, metalli pesanti e carbonio, rappresentano degli interessanti indicatori del contesto ambientale, in particolare della qualità dell’aria, e della stabilità chimica delle fasi mineralogiche della trachite e delle malte di allettamento usate sulla pietra. Infine, la durevolezza della trachite è stata esaminata attraverso una caratterizzazione petrofisica e meccanica di campioni di cava, fornendo elementi utili alla valutazione della qualità da parte di restauratori, conservatori e compagnie edili. Particolare attenzione è stata riservata alla valutazione delle proprietà legate all’assorbimento, movimento e permanenza nella pietra dell’acqua e di soluzioni acquose, allo stato liquido e gassoso. I risultati sperimentali suggeriscono che la variabilità nella resa fisico-meccanica di diversi tipi di trachite dipende primariamente dalle peculiari caratteristiche porosimetriche (volume, dimensione, distribuzione dimensionale, morfologia e grado di interconnessione dei pori), che contribuiscono quindi a determinare diversi gradi di resistenza al degrado.

ABSTRACT: In this investigation, a protocol combining the use of Monte Carlo simulations together with energy-dispersive X-ray fluorescence (ED-XRF) analysis was used to determine the chemical composition of a set of nine objects from a private collection, apprehended by Carabinieri and without archaeological context. The artefacts are thought to belong to the nuragic period from Sardinia, Italy. The protocol employed is a powerful and non-destructive method useful for cultural heritage applications where usually no sampling is allowed and was applied here with the objective of attesting the authenticity of the objects. The samples were simulated as multilayered structures composed of bulk material and outer corrosion layer so the patina thickness and composition could be estimated as well by the Xray Monte Carlo (XRMC) package. The method proved useful and powerful, capable of efficiently determining the composition and structure of most of the objects in a total nondestructive approach, attesting the existence of at least one fake in the set. Nevertheless, for a more throughout evaluation and a better estimation of the patina composition, the use of complementary analytical techniques has shown required.

A presente pesquisa, partiu de uma problemática relacionada ao conceito de cadeias operatórias e propôs avaliar a existência de conexões entre os vasilhames e as fontes de matéria prima, além de constatar o emprego de tempero enquanto dado cultural na pasta cerâmica, buscando suporte para obtenção de respostas numa ampla gama de análises arqueométricas. Desenvolvida nos sítios Inhazinha e Rodrigues Furtado, localizados no município de Perdizes no Triângulo Mineiro, a pesquisa evidenciou uma nova zona arqueológica para o sítio Inhazinha, que se caracteriza por um sistema de produção cerâmica composto por três fornos escavados, associado a um horizonte cultural (agricultores ceramistas históricos) até então desconhecido para a região de estudo. Datada em 212±19 anos AP (AMS-CENA-USP/SP), e 190±30 anos AP (C14-BETA/EUA), tal assentamento, se constitui de uma nova ocupação relacionada aos Cayapós Meridionais que viveram na região do Triângulo Mineiro até o final do século XIX. Os vestígios encontrados, revelam não só as características socioculturais do grupo, mas também demonstram processos de \"interação\" decorrentes do inevitável contato com o homem branco. Os resultados obtidos por meio de estudos arqueométricos demonstram que os vasilhames cerâmicos não possuem correlação com as fontes argilosas evidenciadas no entorno de cada um dos sítios arqueológicos. Constatou-se a ocorrência de tempero enquanto dado cultural na cerâmica da Zona 02 do sítio Inhazinha, constituído pela inserção de materiais granulados de formas hexagonais e retangulares, aparentando ossículos de peixe que ao serem analisadas por meio da microscopia eletrônica de varredura - MEV, confirmou se tratar de material orgânico calcinado com alto teor de carbono.
This research started from a problem related to the concept of operational chains and proposed to evaluate the existence of connections between the ancient pottery and the sources of raw materials, apart from finding employment seasoning as cultural data in ceramic slurry, seeking support for obtaining responses in a wide range of archeometric analysis. Developed in Inhazinha and Rodrigues Furtado sites, located in the Perdizes municipality in Minas Triangle, the research showed a new archaeological zone for the site Inhazinha, which is characterized by a ceramic production system consists of three excavated ovens, associated with a cultural horizon (Historic potters farmers) hitherto unknown to the study region. Dated at 212 ± 19 years BP (AMS-CENA-USP/SP), and 190 ± 30 years BP (C14-BETA/USA), such settlement, constitutes a new occupation related to Southern Cayapós who lived in the Triangle Mineiro region until the late nineteenth century. The remains found, reveal not only the sociocultural characteristics of the group, but also demonstrate processes of \"interaction\" resulting from unavoidable contact with the colonizer man. The results obtained by archaeometric studies show that ceramic pottery have no correlation with clay sources highlighted in the vicinity of each of the archaeological sites. It was found the occurrence of temper as cultural data on ceramics Zone 02 Inhazinha site, consisting of the insertion of granular materials of hexagonal and rectangular shapes, looking fish ossicles that when analyzed by scanning electron microscopy - SEM confirmed it is calcined organic material with high carbon content.

O presente trabalho tem por objetivo caracterizar e identificar a natureza de recursos cerâmicos brasileiros utilizando métodos físicos não destrutivos. O estudo está inserido na área interdisciplinar da Arqueometria e envolve a participação de pesquisadores do Museu de Arqueologia e Etnografia da Universidade de São Paulo (MAE-USP). As amostras analisadas são de grande interesse arqueológico, pois foram coletadas em uma região do Pantanal sul-matogrossense que possui um complexo processo de ocupação envolvendo diversas tradições culturais, entre as quais a tradição Guarani e a tradição Pantanal. Os fragmentos cerâmicos foram caracterizados através das técnicas de Emissão de Raios X Induzido por Partícula (PIXE) e Fluorescência de Raios X (XRF) para a determinação da composição da matriz da pasta cerâmica e através da técnica de Radiografia Computadorizada para a investigação da estrutura interna das peças. A técnica PIXE permitiu uma caracterização dos elementos majoritários encontrados na matriz cerâmica (Z<26), usados na previsão do valor da densidade da matriz. A técnica XRF foi utilizada para determinar as concentrações elementares com destaque para os elementos minoritários (Z>26, wt%<5%) presentes na pasta cerâmica. Essas técnicas, quando associadas a métodos de análise estatísticos permitiram um melhor entendimento do conjunto de amostras. Os resultados encontrados apontam uma clara diferença na composição elementar das amostras encontradas nos diferentes sítios arqueológicos e pertencentes às diferentes tradições. Com a aplicação da técnica de Radiografia as amostras foram separadas de acordo com a presença de tempero em sua estrutura e através da análise das imagens radiográficas foi determinada a densidade dos fragmentos. Neste trabalho foi possível estabelecer uma relação entre os fragmentos cerâmicos estudados às suas tradições, assim como aos sítios arqueológicos nos quais foram coletados.
The present work aims to characterize and identify the nature of Brazilian ceramics using non-destructive physical methods. The study is inserted in the interdisciplinary area of the Archaeometry and involves the participation of researchers from the Museum of Archaeology and Ethnography of the University of São Paulo (MAE-USP). The analyzed samples are of great archaeological interest, as they have been collected in a region of Pantanal in the state of Mato Grosso do sul with a complex settlement process that involves different cultural traditions like the Guarani tradition and the tradition Pantanal. The ceramic fragments were characterized through the techniques of X-ray Emission Particle-Induced (PIXE) and X-Ray Fluorescence (XRF) to determine the composition of the matrix of the ceramic paste and using the technique of Computed Radiography for the investigation of internal structure of the sherds. PIXE technique allowed a characterization of majoritarian elements found in ceramic matrix (Z < 26) and was used in the prediction of the density of the paste. XRF technique was used to determine the elemental concentration with emphasis on the minority elements (Z> 26, wt% < 5%) presents in ceramic paste. These techniques, when associated with statistical methods of analysis allow a better understanding of the sample set. The results show a clear difference in the elemental composition of the samples found in different archaeological sites and from different cultural traditions. By applying the technique of X-ray samples were separated according to the presence of temper in its structure and through images was obtained the density of fragments. In this work it was possible to establish a link between the studied ceramic fragments to their traditions, as well as the archaeological sites in which they were collected.

Em arqueometria e nas ciências aplicadas, metodologias físicas e químicas são de grande utilidade para estudar diferentes materiais e objetos do patrimônio cultural como pinturas de cavalete, murais, cerâmicas, metais, etc. No caso particular de pinturas, tais análises podem auxiliar na compreensão do processo criativo, dos materiais utilizados pelo artista e do estado de conservação desta obra. No contexto deste último item, podem ser caracterizados sinais de degradação, como a alteração de cores. Dentro do objetivo de compreender a degradação de alguns pigmentos por exposição luminosa, estudaram-se os pigmentos amarelo de cádmio (CdS), amarelo de cromo (PbCrO4), azul de cobalto (CoAl2O4) e cerúleo (Co2SnO4), sendo estes dois últimos também misturados ao branco de zinco (ZnO). Tais estudos foram realizados através de três ensaios com amostras padrões preparadas com estes pigmentos: fotodegradação induzida na linha TGM (Toroidal Grating Monochromator) do Laboratório Nacional de Luz Síncrotron; exposição à luz ultravioleta no simulador solar SOL-UV; e exposição às radiações ultravioleta, visível e infravermelha em uma câmara projetada neste mestrado. Os resultados apontaram para indicativos de alteração em todas as amostras, em especial mudanças no espectro de reflectância na região do visível. Por fim, analisaram-se amostras de tintas obtidas de obras do pintor Candido Portinari que possuíam indícios de alteração cromática. A partir destes fragmentos, construíram-se modelos estratigráficos dos materiais utilizados pelo artista nestas pinturas.
In archeometry and applied sciences, physical and chemical methodologies are very useful for studying different materials and objects of cultural heritage such as easel paintings, murals, ceramics, metals, etc. In the particular case of paintings, such analyses can help in understanding the creative process, the materials used by the artist and the conservation status of this work. In the context of this latter item, signs of degradation, such as color change, can be characterized. In order to understand the degradation of some pigments by light exposure, the cadmium yellow (CdS), chrome yellow (PbCrO4), cobalt blue (CoAl2O4) and cerulean blue (Co2SnO4) pigments were studied, the latter two being also mixed with zinc white pigment (ZnO). Such studies were carried out through three experiments prepared with these pigments: photodegradation induced in the TGM (Toroidal Grating Monochromator) line of the National Laboratory of Synchrotron Light; exposure to ultraviolet light in the SOL-UV solar simulator; and exposure to ultraviolet, visible and infrared radiation in a chamber designed in this master\'s degree. The results pointed out changes in all samples, especially in their reflectance spectrum in the visible region. Finally, samples obtained from works by the painter Candido Portinari that had signs of chromatic alteration were analyzed. Based on these fragments, stratigraphic models of the materials used by the artist in these paintings could be constructed.

Two plazas at Cobá, Mexico, may have been the place of market activity during the classic Maya period. The intense decomposition in the warm, moist soils of the Yucatan Peninsula precludes the identification of organic artifacts in archaeological contexts, but phosphorus and trace elements accumulation in soils may provide evidence of marketing activities. The spatial patterns of P and trace element concentrations were used to elucidate the types of ancient Maya activities that took place in those plazas. Phosphorus concentrations are highly correlated (p-value <0.01) with Fe, Mn, and Zn levels in both Plaza B and D. Although the soil geochemistry of Plaza B does not show a marketplace pattern in comparison with previous studies, the elemental concentrations and distributions within Plaza D join other lines of evidence to support the premise that marketplace activities took place at that location. Soil samples were analyzed using DTPA extraction, Mehlich II, Olsen, and Portable X-Ray Fluorescence (PXRF). Experiments were performed to study the suitability of PXRF for field studies. Aspects that were studied include granule size, soil moisture content, protective plastic films that could interfere with the X-Ray signal when placing the samples on top of the analyzer, and a comparison of certified soil standards to the PXRF elemental concentration readings. The results suggest that a field laboratory could be set up to air-dry and sieve soil samples to a minimum mesh size of #10 (> 2 mm).

The Etruscan civilization was rich in local and interregional trade. Its exchange networks were vital in establishing relationships with other societies, importing exotic materials and goods, as well as disseminating and assimilating information. However, there is little understanding of the participation of smaller inland settlements in the act of exchange. This research answers questions pertaining to the purpose of trade within these self-sustaining communities, the reliability of identifying geographic locations of the clay used in ancient ceramics through the use of non-destructive X-ray Fluorescence (XRF) spectrometry without sampling current regional clay sources, and the materiality of the ceramics being exchanged in order to establish major forms of production for each settlement. The analyses of trace elements contained within the ceramic materials previously excavated from two remote Etruscan sites (La Piana and Cetamura) can provide a greater understanding of both the trade practices of the Etruscan culture and the reliability of the sourcing methods. Over 100 ceramics ranging from storage containers, bricks and roofing tiles, amphorae, loom weights, and tableware (including red and black gloss) from Cetamura and La Piana were selected to represent a sample base for local and non-local crafted ceramics. The artifacts were analyzed non-destructively using a Bruker Tracer III-SD portable X-ray fluorescence spectrometer (pXRF), which has been shown to be highly successful in other archaeological studies. Six trace elements (rubidium, strontium, yttrium, zirconium, niobium and thorium) of each artifact were recorded and analyzed using principal component analysis to create a comparable data set. The results confirm that while these Etruscan settlements were self-sustaining, they were still participating in long-distance exchanges.

Throughout history and prehistory, Sicily has played a key role for maritime trade in the Mediterranean. Interactions with Sicily are attested to in research for various societies throughout the Mediterranean as early as the Neolithic. However, much of this research paints Sicilian societies as passive, focusing primarily on external groups of people in a given period and their influence on the island. By ignoring the importance of the indigenous population, current research lacks a balanced approach to investigations and subsequent conclusions. This is most evident in literature pertaining to Mycenaean interactions with Sicily during the Bronze Age. Ceramic evidence and archaeometric studies can be used to reveal the impetus and scope of these interactions. This research addresses the nature of exchange in Bronze Age Sicily prior to Mycenaean influence. In addition, my research addresses apprehensions regarding the precision of portable X-ray fluorescence (pXRF) analysis on archaeological ceramics. Samples of Bronze Age ceramics from eight archaeological sites in southern Sicily were analyzed using non-destructive pXRF spectrometry. Multiple single spot and multi-spot analyses were conducted to assess the precision of the device and the non-destructive application of the technology on potentially heterogeneous materials. Findings show no significant difference in trace element composition levels with either method. Regional signatures of ceramic trace element compositions may be developed and used to assess existing exchange patterns in Bronze Age Sicily. Comparison of ceramic exchange patterns between the Early and Middle Bronze Age suggests that Sicilian populations had a strong local identity and were noticeably inter-connected prior to Aegean influence.

Parmi les matériaux qui ont été exploités dans l'Antiquité, les substances organiques sont probablement les plus difficiles à étudier en raison de leur altération partielle ou totale en raison de leur nature organique. Issus de biomatériaux organiques tels que les résines, la cire d'abeille, les graisses animales ou les huiles végétales, ils sont conservés en faible quantité comme résidus organiques amorphes et sont souvent difficiles à détecter sur le terrain archéologique. Ils témoignent de l'utilisation de produits d'origine animale, végétale et fossile qui ont une grande importance pour divers aspects de la vie humaine, notamment l'alimentation, la médecine, les rituels funéraires, ainsi que les activités économiques et techniques. Comme ils n'ont pas d'attributs morphologiques reconnaissables, la seule façon de déterminer leur nature et leur origine repose sur l'élaboration de stratégies analytiques qui permettent d'élucider leur composition chimique. Ces substances ont des caractéristiques communes dans le domaine de l'archéologie et de la chimie : elles sont constituées de mélanges moléculaires complexes qui sont souvent conservés en faible quantité. Dans certains cas, ces matériaux ont été mélangés avec divers adjuvants tels que la cire d'abeille, les huiles végétales, les graisses animales, l'argile et l'ocre, entre autres, qui devront également être pris en considération pour la caractérisation des objets qui appartiennent au patrimoine culturel. Nous concentrons nos recherches sur les exsudats et les goudrons de plantes frais et fossiles qui ont été largement utilisés depuis la préhistoire en Europe. Concernant l'étude des substances organiques fraîches, des recherches ethnoarchéologiques ont été menées en collaboration avec le projet ONGUENT (Goudrons végétaux à usage médicinal en Méditerranée : passés et présents. Burri, Sylvain/Traces, Toulouse) afin d'identifier et de caractériser la composition chimique et d'établir les biomarqueurs des goudrons de conifères ethnoarchéologiques de Cupressaceae et Taxaceae (Juniperus oxycedrus, Juniperus thurifera, Taxus baccata, Tetraclinis articulata) provenant de techniques anciennes du Haut Atlas au Maroc. En comprenant les méthodes de fabrication des échantillons ethnoarchéologiques et en évaluant les différentes techniques employées dans leur production, il est possible d'obtenir des données de référence sur les matériaux contemporains. D'autre part, des échantillons archéologiques ont été analysés sur différents sites entre l'Europe et l'Asie au moyen des méthodes FTIR, SEM, DI-MS, et GC-MS. La caractérisation biomoléculaire de produits naturels tels que le goudron d'écorce de bouleau et la résine de pin a été soulevée. Par ailleurs, des mélanges de résine de pin avec du goudron d'écorce de bouleau et de résine de pin avec une espèce appartenant à la famille des Burseraceae ont été identifiés
Among the materials that have been exploited in ancient periods, organic substances are probably the most challenging to study due to their partial or total alteration in consequence of their organic nature. Issued from organic biomaterials such as resins, beeswax, animal fats or plant oils, they are preserved in low amount as amorphous organic residues and are often difficult to detect at the archaeological field. They give evidence for the use of animal, plant and fossil products that were of great importance for various aspects of human life, including diet, medicine, funerary rituals, as well as economic and technical activities. Because they lack recognizable morphological attributes, the only way to determine their nature and origin relies on the development of analytical strategies that allow elucidation of their chemical composition. These substances share common features in the field of archaeology and chemistry: they are made of complex molecular mixtures which are often preserved at low amount. In some cases, these materials were mixed with various adjuvants such as beeswax, plant oils, animal fats, clay, and ochre, among others, that will also need to be considered for the characterization of the objects that belong to the Cultural Heritage. We focus our research on fresh and fossil plant exudates and tars that have been largely used since prehistory onwards in Europe. Concerning the study of fresh organic substances, ethnoarchaeological research has been carried out in collaboration with the ONGUENT project (Goudrons végétaux à usage médicinal en Méditerranée: passés et présents. Burri, Sylvain/Traces, Toulouse) in order to identify and characterize the chemical composition and establishing the biomarkers of the ethnoarchaeological conifer tars from Cupressaceae and Taxaceae (Juniperus oxycedrus, Juniperus thurifera, Taxus baccata, Tetraclinis articulata) obtained from antique techniques in the High Atlas, Morocco. By understanding the manufacturing methods of ethnoarcheological samples and to assess the different techniques employed in their production, it is possible to obtain a reference data on contemporary materials.On the other hand, archaeological samples were analyzed from different sites between Europe and Asia by means of FTIR, SEM, DI-MS, and GC-MS methods. Biomolecular characterization of natural products such as birch bark tar and pine resin were raised. Besides, mixtures between pine resin with birch bark tar and pine resin with a species belonging to the family of Burseraceae were identified

In this study, two sample sets from Zeugma Archaeological Area had been examined. The sample Set I includes 7 sediment, 18 stone, 4 brick/roof tile, 9 mortar, 4 plaster samples and the sample Set II consists of 24 mural painting samples. Samples were examined to get their raw material characteristics, mineralogical and chemical compositions, and microstructural properties using various analytical techniques such as Optical Microscopy, XRD, FTIR, PED-XRF, SEM-EDX and Raman Spectroscopy. In addition, mikroclimatic monitorings for temperature and relative humidity were also performed in that area. Sediments were calcereous soils of Eocene. Rock types of stones were mainly limestone which had 3 subgroups: micritic, biomicritic and recrytallised micritic limestones. The source of the limestones should be from the local formation. The firing temperature of brick/roof tile samples were estimated as 800-850°
C. Binder of mortar samples were mainly lime. Aggregate materials of brick/roof tiles, mortars, plasters and mural paintings may come from the river deposites of Euphrates. Mural painting samples have one intonaco layer, and single or double arriccio layers. The mural painting technique was fresco technique. Calcite was common mineral identified for all pigments. The sources of white, black and green coloured pigments were found as vaterite, graphite and malachite respectively. The sources of yellow coloured pigments were identified as ankerite, siderite and goethite. The red colours were identified as hematite, jasper and red earth/ochre. Jasper and vaterite, jasper and calcite, red earth/ochre and calcite, and hematite were the colour forming minerals of pink coloured pigments.

This research evaluates the degree of political integration in Colima during the Late Classic/Epiclassic period (550-1000 CE) and the historical depth of three 16th-century regional polities through an examination of the political strategies embedded in pottery technology. Pottery samples covering three regional polities (Provincia del Colimotl, Valle de Tecomán, Provincia de Tepetitango) and corresponding to four geographical micro-regions (Colima Valley, Salado River basin, Tecomán coastal plain, western coast) were analysed. In this research, polities are conceptualised as webs of authoritative relationships, which are created and contested by political strategies. Pottery produced in the same polity should therefore be in the same network of authoritative relationships. Political strategies are uncovered by identifying the technological patterns, material and socio-technological constraints of production, sourcing-distribution patterns, organisation of production, and social contexts of the consumption of pottery. Compositional and fabric variability was assessed through the archaeometric characterisation of 215 pottery samples from 17 different sites distributed throughout the research area. The statistical analysis of the geochemical results revealed 10 compositional groups; an eleventh group was identified through petrographic analysis. Pottery and raw clay (14 samples) compositional data, together with the analysis of distribution patterns and the local geology, permitted the identification of the location (at the micro-regional level or less) of clay sources for seven of the compositional groups. The room left for technological choices/styles was determined through reconstruction of the pottery production sequence within its contextual factors. The results indicate that pottery production was not centralised, even at the micro-regional level. Potters from the four geographical micro-regions used different clay sources to produce both distinctive wares and some shared types. However, with the probable exception of the Colima Valley, at least a couple clay sources were simultaneously exploited in each micro-region. In some instances, this reflects product specialisation; in others, it indicates production of the same pottery types by competing workshops. Though the two geographical micro-regions in the Provincia del Colimotl did not escape the micro-regional pattern of the use of local resources and manufacture of distinctive wares, they do offer the only example of pottery-related, deliberate economic interdependence in this study. The pottery was produced by independent specialists who made use of distribution networks restricted to the limits of each polity. However, the red-on-cream jars made in the Salado River basin were widely distributed throughout all of the regional polities. It is argued that these jars were obtained at the Salado River basin during communal feasts that involved the consumption of pulque. The results indicate the historical depth of the known 16th-centruy regional polities. Despite providing evidence for close interregional interactions and shared ideological beliefs and social practices within the whole Colima region, pottery analysis offers no solid proof that Colima functioned as a single polity during the Late Classic/Epiclassic period.

Existe um amplo debate sobre as influências culturais remotas nos Andes e o surgimento da cerâmica nesses contextos. Nosso estudo não pretende retroceder aos períodos Formativo ou Cerâmico Inicial, mas apenas situar a coleção de cerâmica chimu do MAE/USP em relação ao debate atual sobre as relações de continuidade ou descontinuidade na costa norte peruana, através do estudo da tecnologia de produção cerâmica. O sistema tecnológico que caracteriza essa produção geralmente aparece na bibliografia com ênfase nas características de moldagem de seus artefatos e a vasta produção cerâmica desse período raramente é estudada a partir de sua variabilidade tecnológica. Este estudo busca enxergar possíveis diferenças tecnológicas que possam existir por trás dessa mensagem de unicidade e homogeneidade, explícita na cerâmica chimu, e investigar a respeito do significado das escolhas tecnológicas que caracterizam esse processo. A escolha de uma coleção de peças inteiras, de um estilo cerâmico monocromático, coletadas provavelmente aleatoriamente e carente de informação contextual impôs a necessidade de pensarmos numa metodologia diferenciada para a investigação das escolhas tecnológicas. A combinação da análise macroscópica de aspectos morfológicos e iconográficos, com a investigação sistemática através de técnicas físico-químicas não destrutivas permitiu o aprofundamento no conhecimento da tecnologia e especificidades do processo de produção dos artefatos, ao fornecer dados que foram fundamentais para inferências dos aspectos culturais das escolhas tecnológicas associadas a essa coleção.
There is a wide debate on the remote Andes cultural influences and the appearance of ceramics in these contexts. Our study does not intend to go back to Formative periods, but only to retrieve the collection of Chimu pottery MAE / USP with respect to the current debate regarding the relative continuity or discontinuity in Peru\'s northern coast, through the study of ceramic production technology. The technological system that characterizes this production usually appears in the literature with emphasis on the characteristics of molding and the vast production and ceramic artifacts from this period is rarely studied from its technological variability. This study aims to see the future technological differences that may exist behind this message of unity and homogeneity, explicit in Chimu ceramics, and inquiring into the meaning of technology choices that characterize this process. The choice of a collection of whole pieces of a ceramic style monochrome, probably collected at random and lacking in contextual information imposed the need to devise a methodology for the investigation of different technology choices. The combination of macroscopic analysis of morphological and iconographic, with the systematic investigation by physico-chemical techniques non destructive has allowed the depth knowledge of technology and the particularities of the production of the artifacts, to provide data that were fundamental to infer cultural aspects of technology choices associated with this collection.

Os sítios arqueológicos de Sumhuram (séculos III a II aC - início V dC) e Inqitat (primeiro milénio aC - séculos I a II dC) estão envolvidos num dos exemplos mais importantes de rede de comércio a grande escala na antiguidade: a rede de comércio marítimo no Oceano Índico. Ambos, localizados na Província de Dhofar (Omã), ao longo do Wadi Darbat, estiveram diretamente envolvidos neste intercâmbio, sendo um exemplo extraordinário da sua complexidade. A atenção deste trabalho está focada na caracterização do material cerâmico Local e Indiano, de ambos os locais, abrangendo idades desde o final do primeiro milénio aC até ao século IV dC. Realizou-se uma abordagem multi-analítica complementar com o objetivo de caracterização das cerâmicas e validação das proveniências resultantes da abordagem tipológica. As técnicas utilizadas na análise foram Difração de raio-X (XRD), Análise Petrográfica, Espectrometria de massa por plasma acoplado indutivamente (ICP-MS), perda ao rubro (LOI) e Microscopia eletrónica de varrimento acoplado a espectroscopia de energia dispersiva de raios-X (SEM- EDS). Os resultados obtidos identificam 8 grupos distintos com base na composição-fabric (desengordurante rico em conchas (ST), desengordurante rico em argilito (SF), fabric rico em talco (TF), fabric rico em basalto (BF), desengordurante rico em arroz (RT), material fino (FF), desengordurante médio-grosseiro em fabric fino (MLF) e desengordurante rico em conchas e areia (SSF)) traduzindo assinaturas geológicas muito distintas e destacando assim a enorme variabilidade na origem das matérias-primas. A maioria dos grupos tipológicos definidos como Indianos são aqui confirmados como provenientes do subcontinente indiano, mas a classificação tipológica existente não reflete o agrupamento fabric-composicional. Dentro dos grupos Locais (ST, SF e TF), a presença do grupo de cerâmica rica em talco (TF) e proveniente do Iémen levanta a discussão sobre o significado de “Local”. Embora não seja possível associar diferentes matérias-primas com rotas comerciais estabelecidas, a variabilidade dos grupos indianos identificados implica a participação de várias áreas do subcontinente indiano na rede de comércio do Oceano Índico: Gujarat e a região centro-oeste, sul da Índia, Sri Lanka e a planície aluvial do norte da Índia. Os resultados destacam a grande extensão geográfica da rede de comércio, mas mais importante, sublinham o papel fundamental da abordagem multi-analítica no apoio à identificação de proveniências, representando o ponto de partida para uma nova abordagem de base científica para o fenómeno da globalização do Oceano Índico; Abstract: Multi-analytical characterization of ceramics from Dhofar (Southern Oman): provenance and trade. The archaeological sites of Sumhuram (3rd -2 nd century BC until the early 5th century AD) and Inqitat (1st millennium BC until the 1st -2 nd century AD), are involved in one of the most important examples of large-scale trade network in the antiquity: the maritime trade network connecting the coasts of the Indian Ocean. Both sites, located in the Governorate of Dhofar in Oman, along the Wadi Darbat, were directly involved in the network being an extraordinary example of its complexity. The attention of this work is focused on the material characterization of both local and Indian pottery from both sites spanning from the late 1st millennium BC until the 4th century AD. A multianalytical complementary approach was carried out in order to characterize the ceramics and validate the provenance identification resulting from the typological approach. The techniques used in the analysis are X-Ray Diffraction (XRD), petrographic analysis, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Loss on Ignition (LOI) and Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectroscopy (SEM-EDS). The results obtained identify 8 different fabric-compositional groups (Shell-Temper (ST), Shalerich Fabric (SF), Talc-rich Fabric (TF), Basalt-rich Fabric (BF), Rice Temper (RT), Fine Fabric (FF), Medium-Large temper grains in fine Fabric (MLF) and the Shell and Sand rich Fabric (SSF)) with very distinct geological signatures highlighting the enormous variability in the origin of raw materials. Most of the typological groups defined as Indian are here confirmed as actually from India, but the specific typological classification does not reflect the fabric grouping. Within local groups (ST, SF and TF) the presence of a pottery group (TF) coming from Yemen raises the discussion about the meaning of “local”. Although it is not possible to associate different raw materials with specific known commercial routes, the variability of the Indian fabric-compositional groups indicates the participation of several areas of the Indian subcontinent in the Indian Ocean trade network: Gujarat and the central-west region, south of India, Sri Lanka and the alluvial plane of the north of India. The results highlight the large geographical extension of the trade network, but, more importantly, they underline the fundamental role of multi-analytical approach in support to the provenance identification representing the starting point for a new scientific-based approach to the Indian Ocean globalisation phenomenon.

Abstract: This research presents the first archaeometric investigation on Damirgaya and Trialeti Rock art sites and the Neolithic settlement Khramis Didi Gora, South Caucasus, Georgia. The aim is to characterize rocks and pigments, to assess painting technology, including the possible identification of organic binders and the compatibility of inorganic pigments with those locally available. In order to build up our awareness and solve scientific curiosity, the research questions are cleared up through the comparison with adjacent archaeological sites, from Armenia, Azerbaijan and Anatolia, where traces of monochromatic red pigment were recovered in settlements, barrows, on artifacts, such as grinding tools and mainly on rock art. Several analytical techniques, specifically Optical Microscopy (OM) on samples as such and thin sections, X-ray Powder Diffraction (XRPD), and Scanning Electron Microscopy with Energy Dispersive X-ray analysis (SEM-EDX) were used to obtain mineralogical and chemical composition of the samples. Moreover, with the contribution of Fourier-Transform Infrared (FTIR) and Raman Spectroscopy, inorganic compounds were better characterized in both rock paintings and grinding tools. On the contrary, it was not possible to define organic compounds such as binders, possibly due to their low amount or absence. In terms of compatibility with local supplies, with the help of thin section and cross section analysis, it was possible to deduce that the mineralogical composition of the rocks is relatively similar to pigment samples. In terms of pigments, hematite was the major pigment used for rock art and grinding tools, while in terms of rock samples, that of Trialeti is an igneous basaltic dacite, whereas that of Damirgaya is a rock mainly composed of quartz, but it is also characterized by other minerals, such as iron oxides are likely present, as well as phyllosilicates.

O presente trabalho teve como objetivo estudar sobre o modo de produção da cerâmicas arqueológicas da T. I. Koatinemo, e desse modo oferecer mais informações sobre o longo e contínuo processo de ocupações indígenas da Amazônia. A partir da caracterização arqueométrica dos fragmentos de vasilhas algumas questões foram investigadas como: quais foram as escolhas das fontes argilosas feitas pelos ceramistas, como foi o processo de manufatura e qual temperatura máxima na qual as peças foram queimadas, bem como sobre qual é a performance final das vasilhas. Os equipamentos utilizados foram a Fluorescência de Raios X, a Difração de Raios X, a Radiografia, a Microscopia Eletrônica de Varredura e a Petrografia. Assim, a partir das características físicas, químicas e mineralógicas das peças, muito pode ser entendido sobre os comportamentos dos antigos ceramistas, bem como sobre os grupos indígenas a que pertenciam.
The present work aimed to study the production process of I. L. Koatinemo\'s archeological ceramics, and thus to offer more information about the long and continuous process of indigenous occupations of the Amazon. From the archaeometric characterization of the pot fragments, some questions were investigated such as: what were the choices of the clay sources doneby the ceramists, the manufacturing process and the maximum quality in which the pieces were burned, as well as what resulted as a final performance of the vessel. The equipments used were X-Ray Fluorescence, X-Ray Diffraction, Radiography, Scanning Electron Microscopy and Petrography. Thus, from the physical, chemical and mineralogical characteristics of the pieces, much could be understood about the behaviors of the ceramists, as well as about the indigenous groups that they belonged to.

The Corsican Bronze Age is characterized by the erection of massive stone towers, the torre, and of stone enclosures, the casteddi. While the role of these structures is still debated, they have generally been interpreted as the sign of a hierarchical society, pervaded by martial values and fragmented into competing antagonistic groups. After several centuries of stability, a sharp demographic decline occurred at the end of the Middle Bronze Age. ca. 1350 and 1200 BC. In contrast, the Final Bronze Age, between 1200 and 950 BC, is a period of continuous expansion, characterized by the appearance of new forms of cultural expression, which included the erection of armed menhirs, the development of open villages, and the manufacture of a new type of ceramic production, manifestly inspired by foreign models. The aim of this work is to improve our understanding of the social dynamics at work during the Final Bronze Age through the study of the mobility of the ceramics within a systemic theoretical framework. Another goal is to further our understanding of the function of the fine ware during this period. A portable X-ray fluorescence spectrometer (pXRF) was used on 321 ceramic artifacts from six different sites to assess the extent of the exchanges taking place between six sites, located both on the inner plateaus and the coastal plains. Ceramics made from non-local clay material are present at five out of six sites, which shows that economic exchanges regularly took place between different communities. Except for one site, there is no association between a specific clay material and a type of ware. These results suggest that Final Bronze Age Corsican society should be considered as largely open to external influences.

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Intervenções realizadas no Sítio Arqueológico Pedra do Alexandre resultaram na exumação de vestígios ósseos pertencentes a pelo menos 36 indivíduos humanos. Datações radiocarbônicas de carvões vegetais associados forneceram dados para o estabelecimento de uma cronologia de ocupação do sítio entre 9400 e 2620 anos antes do presente, ainda que possivelmente não contínua. No entanto, tentativas de se datar diretamente os indivíduos mostraram-se infrutíferas devido às perdas de colágeno provocadas por processos diagenéticos. A partir desta constatação deu-se início à investigação para saber o que ocasionou tais processos ao mesmo tempo em que foi experimentada a datação direta de um dos indivíduos mediante emprego da espectroscopia de RPE. Com a realização de espectroscopias no infravermelho e difrações de raio-x em amostras ósseas dos indivíduos foi possível constatar que todas apresentavam extensa perda de colágeno. Medições do pH de sedimentos associados levaram a concluir que o principal causador destas perdas teria sido uma intensa atividade microbiana no sedimento e não a ocorrência de hidrólises ácidas, como era pensado inicialmente. O experimento de datação foi realizado com dificuldade devido à pequena dose de radiação na amostra, o que indicaria a pouca idade da mesma, provavelmente posicionada na metade mais recente do intervalo cronológico já estabelecido para a ocupação do Sítio. A partir destas análises amostrais é possível concluir que todo o conjunto de vestígios ósseos do referido sítio deve ter sido diageneticamente alterado. A espectroscopia de RPE por sua vez mostra-se capaz de datar plenamente dentes provenientes dos indivíduos exumados
Archaeological interventions conducted in the Pedra do Alexandre Archaeological Site resulted in the exhumation of skeletal remains of at least 36 human individuals. Radiocarbon dating of associated charcoals provided data for the establishment of a site occupation chronology between 9400 and 2620 years before present, although possibly not continuous. However, attempts to direct date the individuals proved fruitless due to the loss of collagen caused by diagenetic processes. From that finding, this research was initiated to know what caused these processes at the same time that was tried the direct dating of one individual using EPR spectroscopy. Infrared spectroscopy and x-ray diffraction conducted on bone samples from the individual made it possible to calculate determined diagenetic indices that showed extensive loss of collagen in all the samples. pH measurements in associated sediments indicated the conclusion that the main cause of these losses would have been an intense microbial activity in these sediments, and not the acidic hydrolysis as initially thought. The dating experiment was carried out with difficulty due to the small dose of radiation in the sample, which would indicate the recent age of the tooth, probably posiotioned in the most recent half of the chronological range already established for the occupation of the site. From these sample analysis we conclude that the entire set of skeletal remains of the said site must have been diagenetically altered. The EPR spectroscopy in turn proves to be able to fully date teeth from the exhumed individuals.

Neste trabalho foi estudado o efeito sinérgico do microambiente e de óxidos na degradação de corantes e aglutinantes. Para avaliar o efeito de MnO2 e α- Fe2O3 na degradação de aglutinantes em câmaras climáticas à temperatura de 35°C e UR de 50% foi utilizado linoleato de metila como molécula modelo e observou-se que MnO2 atua catalisando reações de auto-oxidação, que ocorrem preferencialmente na degradação desses aglutinantes. Já α- Fe2O3 apresentou comportamento ambíguo, sugerindo mecanismo de ação mais complexo desse óxido. Experimentos para verificar o efeito de luz UV foram conduzidos e reafirmaram os resultados sobre falta de reprodutibilidade dos resultados na presença de α- Fe2O3 e sobre o efeito da presença de MnO2 ser mais significativa para a degradação de linoleato de metila do que a luz. Para gordura vegetal e animal foram conduzidos experimentos com maior tempo de exposição (22 dias), uma vez que não foram observadas mudanças espectrais significativas com 8 dias de exposição. No caso das gorduras animal e vegetal a presença de óxidos de Mn e Fe teve um efeito menos expressivo, mas mesmo assim foi possível observar que o comportamento foi o mesmo do linoleato de metila. No caso dos corantes foi feita uma caracterização espectroscópica de 6 corantes sintéticos semelhantes aos encontrados em têxteis pré-colombianos e avaliou-se a interação de índigo carmim com metais visando mimetizar o comportamento de mordentes proveniente de sais usados como mordentes. Para os corantes índigo carmim, purpurina e alizarina foram estudados os espectros SERS e SERRS, e observou-se que os dois últimos formam complexos com o substrato metálico usado para o obtenção do efeito tendo uma variação significativa em seus espectros Raman. A análise de fibras arqueológicas Huari permitiu identificar que se trata de lã e que o corante da fibra vermelha era carmim.
This work aimed the investigation of the microenvironment and metal ions synergic effect on the degradation of binders and dyes. The role of MnO2 and α- Fe2O3 was assessed using environment chambers at 35°C and 50 % RH and methyl linoleate was chosen as a model binder since fats present very complex chemical composition. It was find that MnO2 catalyses auto-oxidation reactions which are the main routes for binders degradation. On the other hand, the results using α- Fe2O3 were not reproducible, suggesting that this oxide present a more complex mechanism of action. The same behavior was observed when methyl linoleato -metal oxides mixtures were irradiated with UV light and confirms that a radical mechanism mediated the MnO2 catalytic effect. Vegetal and animal fats, although not as sensitive as methyl linoleate to metal oxide, presented the same behavior. The preliminary results on dyes degradation involved the spectroscopic characterization of 6 synthetic dyes, selected from those found in pre-Colombian textiles and indigo carmine metal complexes aiming to mimic mordants. Fe, Cu and Al complexes were prepared and analyzed and complexation only caused minor changes in their spectra compared to indigo carmine. SERS and SERRS were used in the investigation of indigo carmine, purpurin and alizarin and except for the former, the spectra indicated that chemical adsorption to the SERS active surface (Ag and Cu) with a significant change in their spectrum. The analysis of the archaeological Huari fibers allowed to identify that it was wool and the dyes were carmine ( red fiber) and indigo carmine (blue fiber).

Characterization of mortars associated with the hydraulic system of roman villa Horta da Torre (Fronteira, Portugal) Villa Horta da Torre is an archaeological site from the 3rd – 4th century AD located in Fronteira, Portugal. In this Roman site, water plays an important role, due to the fact that the excavated buildings are comprised of a set of structures intended to store and channel water through a series of spaces and areas. This would create the most extraordinary displays to be viewed by a selected and privileged audience. This research aimed to carry out the chemical, mineralogical and microstructural characterization of the lime mortars related to the hydraulic structures from the excavated pars urbana of the villa, in order provide evidence for the assessment of the raw materials used for their manufacture, as well as their provenance, and to establish a chronology amongst the structures. Moreover, valuable information concerning their production techniques was obtained and contrasted with the ancient recipes given by Vitruvius, which can be used for a future outlook with a view to their consolidation and repair. A multianalytical approach was performed to conduct a complete and accurate characterization. Ten samples from hydraulic structures and two additional samples with a chromatic layer were analyzed by means of Optical Microscopy (Stereozoom and Petrographic microscope), X-ray Diffraction (XRD), Variable Pressure Scanning Electron Microscopy coupled to Energy Dispersive X-ray Spectroscopy (VP-SEM-EDS), Thermogravimetric analysis (TGA-DTG), Acid attack and Granulometric analysis. Results demonstrated that the mortars analyzed present remarkable uniformity in terms of chemical, mineralogical and microstructural composition and according to their architectural purpose. There are no variations suggesting a different chronology of their manufacture, so it is assumed that they may be contemporaneous. In terms of production, it is evident that the Vitruvius rules were not followed. It can be implied that masons would have been familiarized with the ancient recipes for construction and the usefulness of ceramics, but this knowledge was always linked to their intuition and to the availability of the materials; RESUMO: Caracterização de argamassas associadas ao sistema hidráulico da villa romana Horta da Torre (Fronteira, Portugal) A villa Horta da Torre é um sítio arqueológico do século III – IV DC, localizado em Fronteira, Portugal. Nesta villa romana, a água desempenhou um papel importante dado que os edifícios são compostos por um conjunto de estruturas destinadas a armazenar e canalizar a água através de uma série de espaços e áreas, o que criaria um ambiente cénico extraordinário para mostrar a um público selecionado e privilegiado. Este estudo teve como objetivo a caracterização química e mineralógica das argamassas de cal relacionadas com as estruturas hidráulicas associadas à pars urbana da villa, a fim de fornecer evidências sobre as matérias-primas utilizadas para sua produção, bem como a sua proveniência, e para estabelecer uma cronologia entre as diferentes estruturas. Além disso, foram obtidas informações relevantes sobre as suas técnicas de produção que contrastam com as receitas antigas indicadas por Vitrúvio, que podem ser consideradas numa perspectiva futura de consolidação e reparação. Efectuou-se uma abordagem multianalítica de modo a obter uma caracterização completa. Foram analisadas dez amostras de argamassas associadas a estruturas hidráulicas e duas amostras adicionais com uma camada cromática, através de Microscopia Óptica (Stereozoom e microscópio petrográfico), Difração de raios X (XRD), Microscopia eletrónica de Varrimento com Pressão Variável, acoplado a Espectroscopia de Energia Dispersiva de raio-X (VP-MEV-EDS), análise Termogravimétrica (ATG-DTG), ataque ácido e análise granulométrica. Os resultados demonstraram que as argamassas estudadas apresentam uma notável uniformidade em termos de composição química, mineralógica e estrutural, e de acordo com seu propósito arquitetónico. Não havendo variações dentro de cada grupo funcional, o que poderia sugerir uma cronologia diferente na sua produção, assume-se que podem ser contemporâneos. Em termos de produção, é evidente que as regras Vitruvius não foram integralmente respeitadas. Os construtores estariam familiarizados com as antigas receitas romanas de construção e com a utilidade da cerâmica, mas esse conhecimento estava sempre ligado à sua intuição e à disponibilidade dos materiais.

This study focuses on the archaeometric characterization of Iron Age to Islamic Period pottery from the archaeological site of Tayma (north-western Saudi Arabia), with the main aim of defining the provenance, the production technology and its evolution over time. This research is part of a joined-project coordinated by the German Archaeological Institute of Berlin and involving the Saudi Arabian Department of Antiquity and the Department of Archaeology and Epigraphy of King Saud University (Riyadh). This project aims to study the material culture as well as the more classical archaeological aspects of Tayma, a site located in the Tabuk province (latitude 27° 37’ N, longitude 38° 28’ E) north-western Saudi Arabia. The importance of the archaeological site of Tayma is related to its almost continuous occupation throughout several millennia. The age of the material here considered is from the Early Iron Age to the Islamic Period. The presence of an important aquifer and a palm grove determined the site to develop and to become a reference point in the trades within the Arabian Peninsula desert steppe area. Numerous attestations indicate that Tayma was involved into commercial and cultural exchanges with the Mediterranean, Mesopotamian, Egyptian and Southern Arabian Peninsula people (Avanzini, 1997, Eichmann et al., 2006, Hausleiter, 2006). In this frame, the ceramic materials play an important role, since the local and regional stratigraphic sequences are based on the continuity versus discontinuity of their typology over time. Therefore, the archaeometrical analysis of the pottery at Tayma can supply important information both on the ceramic production technology as well as on the provenance, allowing the identification of cases of importation and/or local imitation. For this reason, 238 potsherds, 100 from a superficial survey and 138 from stratigraphic contexts dated between Early Iron Age and Islamic Period were studied and compared with a set of clayey and sandy materials collected from the surroundings of Tayma. All the samples were studied in optical microscopy, in order to define homogeneous petrographic groups in terms of groundmass microstructure, textural features and composition of inclusions. The mineralogical and chemical composition of both potsherds from stratigraphic contexts and geological clay samples were determined by X-ray diffraction (XRD) and X-ray fluorescence (XRF), in order to provide constraints to the definition of the firing temperature and possible provenance of the archaeological materials. A multivariate statistical approach was also adopted to process the analytical data with the main aim of distinguishing locally-made and imported objects, and defining the production recipes adopted over time. Detailed analysis of specific microstructures formed during the firing process were also analysed on selected samples in scanning electron microscopy. For this reason, both stratigraphically dated potsherds and clayey materials collected in the surroundings area of the archaeological site were analysed under petrographic, mineralogical, microstructural and chemical viewpoints and the analytical data were processed using multivariate statistical tools. Most of the pottery at Tayma was locally produced according to different recipes, which show a straight correlation with the age. This indicates a systematic change in the pottery production technology over the period of about two millennia here considered. The majority of the pottery is locally produced, and only few ceramic classes, mainly glazed ware, resulted to be imported. On the basis of the mineral-petrographic composition of inclusions and the textural features of the ceramic pastes, 9 main petrographic groups were defined. Group 1 is characterised by fine grained inclusions mostly made of quartz and sometimes sandstone and siltstone rock fragments. The same kind of inclusions was also identified in petrographic group 5, which is however characterized by coarser grained inclusions. Group 2 displays a fine-grained and quartz-poor matrix and bears rare inclusions mostly of argillaceous rock fragments (ARF). Group 3 shows fine to coarse grained inclusions made of ARF, quartz grains and quartz-rich siltstone and sandstone rock fragments. Similar types of inclusions characterise also petrographic group 4, although it is lacking in fine fraction. Group 6 differs from the others for the presence of extremely coarse grained inclusions of quartz and feldspar, while group 8 contains volcanic rock inclusions. Although samples belonging to group 7 display under the optical microscope texture and type of inclusions similar to those of group 1, diffraction patterns show the presence in the matrix of gehlenite, suggesting the presence of carbonate in the original clayey material. Lastly, in potsherds of group 9 the groundmass is almost absent and the inclusions are made of angular grains of quartz. The mineral-petrographic composition of inclusions in the majority of the groups (1, 2, 3, 4, 5) is consistent with the geology of the area surrounding Tayma, which consists of Palaeozoic sedimentary sequences, mainly represented by mudstones, sandstones, siltstones and occasionally limestones containing rare cherts (Le Nindre et al., 2003; Hussain, 2007), associated to Quaternary deposits of sand, often forming large dune systems, and subordinated clays and evaporites. Samples belonging to group 8 are characterised by basalt and acid volcanic rock inclusions which are only outcropping at least one hundred kilometres far from Tayma, as well as those belonging to group 6, the inclusions of which derive from an alkaline granitoid rocks. Therefore on the basis of the mineralogical and lithological match, most of the ceramic pastes were probably locally produced according to different recipes, for which locally available tempers, mainly represented by sand, were added to a clay material. When potsherds are compared with the clay materials from the surrounding of Tayma in terms of chemical composition, it is clear that part of the pottery was imported. Statistical multivariate analysis carried out by the Principal Component Analysis (PCA), revealed that potsherds of groups 1, 2, 3, 4 and 5 form a unique and homogeneous group similar to the clay materials collected in the area, whereas all other groups (6, 7, 8, 9) are chemically not comparable with the clay materials of the area of Tayma, indicating that they were probably imported. Potsherds belonging to group 9 petrographically and compositionally correspond to an islamic stonepaste and an egyptian faience, respectively. Multivariate statistical treatment of chemical data also shows that recipes for the pottery production changed over time, both in terms of abundance and type of temper, and of composition of the starting clayey materials. The chemical compositions of the pottery resulted to lie on mixing trends between possible starting clayey materials and different types of temper, supplying an important tool to better describe tempering processes. As for the firing technology, the mineralogical composition shows that all the potsherds locally produced contain mullite, spinel and quartz. This mineralogical assemblage indicates that the base-clay was kaolinitic in composition and firing temperatures around 1000°C (Aras, 2004). This result is in agreement with the mineralogical composition of the clay materials collected from the surroundings of Tayma, composed of kaolinite and subordinate illite, smectite, quartz and goethite. Some samples of groups 1, 3, 4 and 5 bears vitrified ARFs showing a vesicular texture caused by degassing during melting. The mineralogical assemblage of those samples is characterised by the presence of hercynite and the absence of hematite suggesting firing temperatures exceeding 1000°C (Letsch & Noll, 1983). A few archaeological samples bearing ARFs were fired at 1100°C and 1200°C. The vesicular texture and hercynite-bearing and hematite-free assemblage were reproduced at 1200°C, suggesting that samples containing vitrified ARFs were fired between 1100°C and 1200°C. The mineralogical assemblage of the imported potsherds is very different, since they contain gehlenite and diopside, indicating that a calcareous base-clay was used for their production and that firing was run at temperature above 850°C (Riccardi et al., 1999). When considering the evolution of the production recipes over time, some interesting points arise. In the Early Iron Age potsherds belong to petrographic groups 1 and 3, while during the Late Iron Age new recipes appeared with the presence of the pottery belonging to petrographic groups 1, 2, 3, 4, 5, 6, 7 and 8. This variety of materials suggests both a marked evolution in the pottery production at Tayma and the flourishing of trades and exchanges with other peoples which brought new ceramic objects from abroad.
Questo studio si focalizza sulla caratterizzazione archeometrica di ceramiche datate dall’età del Ferro all’epoca Islamica del sito archeologico di Tayma (nord-ovest dell’Arabia Saudita), allo scopo di definirne la provenienza, le tecnologie di produzione e relativa evoluzione nel tempo. Questa ricerca è parte di un progetto congiunto coordinato dall'Istituto Archeologico Tedesco di Berlino che coinvolge il Dipartimento di Antichità Saudite e il Dipartimento di Epigrafia e Archeologia dell'Università King Saud di Rijad. Questo progetto ha come scopo lo studio della cultura materiale e dei più classici aspetti archeologici di Tayma, un sito collocato nella provincia di Tabuk (latitudine 27° 37’ N, longitudine 38° 28’ E) nel nord ovest dell’Arabia Saudita. L’importanza del sito archeologico di Tayma è da collegarsi alla sua continua occupazione attraverso molti millenni. La presenza di un’importante falda acquifera e lo sviluppo di un vasto palmeto ha determinato lo sviluppo del sito, che si colloca in una posizione strategica lungo le principali vie commerciali nella parte occidentale della penisola arabica. Numerose testimonianze indicano come Tayma fosse coinvolta in scambi commerciali e culturali con le popolazioni del Mediterraneo, della Mesopotamia, dell'Egitto e del meridione della penisola Arabica (Avanzini, 1997, Eichmann et al., 2006, Hausleiter, 2006). In questo contesto, il materiale ceramico gioca un ruolo fondamentale, dato che le sequenze stratigrafiche sia a livello locale che regionale si basano sulla continuità o discontinuità nel tempo delle sue tipologie. Pertanto l’analisi archeometrica della ceramica di Tayma può fornire importanti informazioni sia sulla tecnologia di produzione, che sulla provenienza, permettendo di identificare i casi di importazione e/o imitazione locale. Per questa ragione 238 frammenti di ceramica, di cui 100 provenienti da ricognizione superficiale e 138 da contesti stratigrafici datati tra l’età del Ferro Antico ed il Periodo Islamico, sono stati studiati e confrontati con una serie di materiali argillosi e sabbiosi campionati nei dintorni di Tayma. Tutti i campioni sono stati studiati al microscopio ottico, con lo scopo di definire gruppi petrografici omogenei per microstruttura della pasta di fondo, caratteristiche tessiturali, e composizione degli inclusi. La composizione chimica e mineralogica dei campioni ceramici provenienti da contesti stratigrafici e quella delle argille campionate sono state determinate tramite diffrattometria dei raggi X e fluorescenza dei raggi X al fine di definire le temperature di cottura e la possibile provenienza dei materiali archeologici. È stato inoltre adottato un approccio statistico multivariato per elaborare i dati analitici con lo scopo principale di distinguere tra oggetti di produzione locale e manufatti importati e definire le ricette di produzione adottate attraverso i secoli. Specifiche microstrutture formatesi durante la cottura in determinati campioni sono state inoltre analizzate al microscopio elettronico a scansione. Per questo motivo, le ceramiche provenienti da contesti stratigrafici e quelli relativi alle argille sono stati analizzati da un punto di vista petrografico, mineralogico, microstrutturale e chimico, ed i dati sono stati trattati utilizzando strumenti statistici multivariati. La maggior parte della ceramica di Tayma è stata prodotta localmente secondo diverse ricette, che mostrano una diretta correlazione con le varie epoche storiche. Ciò mostra un cambiamento sistematico nella tecnologia di produzione in un periodo di circa due millenni. Solo poche classi ceramiche, per lo più invetriate, risultano importate. Sulla base della composizione minero-petrografica degli inclusi e delle caratteristiche tessiturali degli impasti ceramici, sono stati individuati nove gruppi petrografici principali. Il gruppo 1 è caratterizzato da inclusi a grana fine costituiti prevalentemente da quarzo e, a volte, da frammenti litici di siltiti ed areniti. Lo stesso tipo di inclusi è stato identificato nel gruppo petrografico 5 che tuttavia è caratterizzato da inclusi a grana più grossolana. Il gruppo 2 mostra una matrice povera in quarzo, ha una grana fine e presenta rari inclusi prevalentemente di rocce argillose (ARF). Il gruppo 3 mostra inclusi di ARF, quarzo e rocce silicoclastiche come siltiti e areniti ricche in quarzo, di granulometria da fine a grossolana. Inclusi simili caratterizzano il gruppo 4 che però manca della frazione fine. Il gruppo 6 differisce dagli altri per la presenza di inclusi di quarzo e feldspati, mentre il gruppo 8 si caratterizza per la presenza di inclusi di rocce vulcaniche. Nonostante i campioni appartenenti al gruppo 7 mostrino al microscopio ottico la tessitura e il tipo di inclusi simili a quelli del gruppo 1, i spettri di diffrazione mostrano la presenza di fasi come la gehlenite, che suggerisce la presenza di carbonati nell'originale materiale argilloso. Infine nel gruppo 9 la pasta di fondo è assente e le inclusioni sono costituite da grani angolari di quarzo. La composizione minero-petrografica degli inclusi della maggior parte dei gruppi (1, 2, 3, 4, 5) è compatibile con la geologia dell'area circostante Tayma, che consiste in sequenze sedimentarie paleozoiche, per lo più rappresentate da argilliti, siltiti e areniti ed occasionalmente da rocce carbonatiche contenenti selce (Le Nindre et al., 2003; Hussain, 2007), associate a depositi quaternari di sabbie che spesso formano ampi sistemi di dune, e secondariamente ad argilliti ed evaporiti. I campioni che appartengono al gruppo 8 sono caratterizzati dalla presenza di inclusi di basalti e di vulcaniti acide, che affiorano solamente a una distanza di almeno cento chilometri da Tayma, così come un campione del gruppo 6, i cui inclusi derivano da rocce plutoniche alcaline. Pertanto, sulla base della corrispondenza mineralogica e litologica, la maggior parte degli impasti ceramici sono stati probabilmente prodotti localmente utilizzando varie ricette secondo le quali al materiale argilloso sono stati aggiunti smagranti disponibili localmente, prevalentemente della granulometria delle sabbie. Comparando la composizione chimica dei frammenti ceramici con quella delle argille provenienti dai dintorni di Tayma, si vede chiaramente come parte dei materiali ceramici siano stati importati. L'analisi statistica multivariata condotta secondo il metodo dell'Analisi delle Componenti Principali (PCA) ha rivelato che i campioni appartenenti ai gruppi 1, 2, 3, 4 e 5 formano un gruppo unico e omogeneo insieme alle argille campionate nella zona, mentre tutti gli altri gruppi (6, 7, 8, 9) sono chimicamente incompatibili con i materiali dell'area circostante Tayma, il che suggerisce che siano di importazione. Le ceramiche appartenenti al gruppo 9 corrispondono petrograficamente e compositivamente a delle Islamic Stonepaste e le Egyptian Faïence (Mason & Tite, 1994; Tite et al. 1983, 1988). Il trattamento statistico multivariato dei dati chimici mostra anche che le ricette per la produzione ceramica cambiò nel tempo, sia in termini di abbondanza e tipologia dello smagrante, che di composizione del materiale argilloso di partenza. La composizione chimica delle argille è risultata giacere lungo linee di mescolamento tra i probabili materiali argillosi di partenza e diversi tipi di smagranti, fornend un importante strumento per una migliore descrizione del processo di tempera. Per quanto riguarda la tecnologia di cottura, la composizione mineralogica mostra che tutti i campioni prodotti localmente contengono mullite, spinello e quarzo. Tale associazione mineralogica indica l'utilizzo di un’argilla caolinitica e temperature di cottura di circa 1000 °C (Aras, 2004). Tale risultato è in accordo con la composizione mineralogica dell'argilla campionata nei dintorni di Tayma, composta da caolinite e, in secondo luogo, smectite, quarzo e goethite. Alcuni campioni dei gruppi 1, 3, 4 e 5 contengono ARF vetrificati, caratterizzati da una struttura vescicolare prodottasi per degassamento durante la fusione. L’associazione mineralogica di tali campioni è caratterizzata dalla presenza di ercinite e dall’assenza di ematite, il che suggerisce temperature di cottura superiori ai 1000°C (Letsch & Noll, 1983). Alcuni campioni ceramici archeologici contenenti ARF sono stati sottoposti a ricottura a 1100°C e 1200°C. La struttura vescicolare degli ARF e l’associazione contenente ercinite e priva di ematite è stata riprodotta a 1200°C, suggerendo che i campioni contenenti ARF vetrificati siano stati cotti a temperature comprese tra 1100°C e 1200°C. L’associazione mineralogica delle ceramiche di importazione è molto diversa da quella delle ceramiche prodotte localmente, ed è caratterizzata da fasi come gehlenite e diopside, che indicano l'utilizzo di un’argilla calcarea e temperature di cottura superiori agli 850°C (Riccardi et al., 1999). Considerando l'evoluzione nel tempo delle ricette di produzione, si evidenziano alcuni punti importanti. Le ceramiche dell’età del Ferro Antico appartengono ai gruppi petrografici 1 e 3, mentre nel Ferro Tardo compaiono nuove ricette riconducibili ai gruppi 1, 2, 3, 4, 5, 6, 7 e 8. Tale varietà di materiale suggerisce sia una evoluzione della produzione locale a Tayma, sia il fiorire di commerci e scambi con altre popolazioni che hanno permesso l’arrivo a Tayma di nuovi oggetti.

La presente tesis doctoral se centra en el estudio de las arquitectura en tierra en contextos de prehistoria reciente (neolítico y edad del Bronce-Hierro) del Próximo Oriente. La necesidad de trabajar con un de los restos materiales más abundantes en el registro arqueológico como es la tierra mediante el adobe, tauf o pisé, entre otros, nos ha llevado a desarrollar un programa analítico complejo que se ha aplicado a 3 yacimientos, dos de ellos situados en Siria (Tell Halula y Tell Tuqan) y otro en Turquía (Yumuktepe). Los tres sitios presentan una cronología distinta que permite caracterizar y comprender la técnica de la construcción del adobe y de los procesos de adquisición de la materia primera, los materiales y los saberes tecnológicos asociados a las construcciones de contextos centrados tanto en el ámbito doméstico como en el público. La introducción de la arqueometría en este campo es una línea de investigación nueva dónde la ausencia de una metodología común no ha permitido la realización de estudios comparativos entre datos de excavaciones distintas y cronología diversa. Por eso en este estudio se ha comparado los tres yacimientos siguiendo una misma propuesta metodológica que se centra en la realización de análisis química-física como DRX, FRX, petrografía, granulometría. Estas técnicas que son las más usadas para caracterizar los materiales y se acompañan de otras pruebas de tipo físico-mecánica como la determinación de porosidad y la determinación de resistencia a través de la prueba de compresión. La naturaleza estructural del material ha llevado a validar el análisis en este sentido. Las muestras procedentes de distintas estructuras domésticas en el caso de Tell Halula (21 muestras) asociadas a grill plan, silos construidos, hornos, hornacinas, canalizaciones, adobes y enlucidos. En el caso de Yumuktepe (17 muestras) y de Tell Tuqan (5 muestra) se han estudiado los adobes asociados a las distintas fases de ocupación con el objetivo de caracterizar los adobes, los suelos de ocupación y los enlucidos de cada periodo. Los resultados han permitido avaluar la hipótesis de un aprovisionamiento local de la tierra que permitirá identificar áreas de captación y zonas de aprovisionamiento asociadas a la gestión y uso del territorio por parte de las comunidades estudiadas. Las pruebas físicas han determinado la diferencia en contenido de agua presente en muestra durante el proceso de elaboración de los adobes. Todas las muestras presentan calcita y cuarzo como mineral mayoritario y otros como feldespatos y mica como minerales secundarios. Esta diversidad de resultados permite identificar estrategias diferenciales en función del elemento construido. A nivel cronológico también se observa que cada solución arquitectónica proviene de una profunda tradición local y difícilmente procede de un saber de nueva adquisición hasta el surgimiento del artesano especialista. Este trabajo ha permitido conocer y profundizar las técnicas de construcción siguiendo un protocolo experimental que tiene como objetivo complementario incidir en los procesos constructivos e inferir en las prácticas de conservación y restauración de los elementos elaborados en tierra cruda.
Questo lavoro di ricerca si centra sullo studio dell’architettura in terra in preistoria e protostoria (Neolitico e Età del Bronzo e Ferro) nel Vicino Oriente. La necessità di studiare uno dei materiali più abbondanti nella documentazione archeologica, com’è la terra, sotto forma di mattone crudo, tauf o pisé, ha permesso di approfondire un programma analitico complesso che si è potuto applicare in tre siti archeologici situati in Siria (Tell Halula e Tell Tuqan) e in Turchia (Yumuktepe). Questi tre insediamenti presentano una cronologia distinta che ha permesso di caratterizzare e comprendere la tecnica della produzione del mattone crudo e dei processi di acquisizione della materia prima, il materiale e il sapere tecnologico associato a la costruzione di differenti contesti come l’ambito domestico e il pubblico. L’introduzione delle indagini archeometriche in questo campo, è una linea di investigazione nuova dove l’assenza di una metodologia comune non ha permesso la realizzazione di studi comparativi tra dati provenienti da scavi archeologici differenti e con cronologia diversa. Per questo, in questo lavoro, sono stati comprati i tre siti archeologici seguendo la stessa proposta metodologica che si è centrata nella realizzazione di analisi chimico-fisiche come la DXR, FRX, petrografia e granulometria. Queste analisi sono le più utilizzate per caratterizzare il materiale terra, e sono avvaliate con altre prove fisiche come la determinazione della porosità , densità apparente e determinazione della resistenza a compressione. La natura strutturale del materiale ha indirizzato le analisi in questa direzione. I campioni sono stati prelevati da distinte strutture domestiche nel caso di Tell Halula (21 campioni) tra grill plan, silos costruiti, forni, nicchie, canalizzazione, mattoni crudi e intonaci. Nel caso di Yumuktepe (17 campioni) e Tell Tuqan (5 campioni) frammenti di mattone crudo prelevato dalle ditinte fasi di occupazione riconosciute, livello di pavimentazione e intonaco. I risultati hanno permmesso di avvalorare l’ipotesi di un approvvigionamento locale della materia prima che permetterà di identificare aree di captazione e di approvvigionamento associate alla gestione e uso del territorio da parte delle comunità studiate. Le prove fisiche hanno determinato la differenza di contenuto di acqua presente nei campioni durante il processo di fabbricazione dei mattoni crudi. Tutti i campioni mostrano calcite e quarzo come minerali maggioritari e altri, come feldspati e mica, come minerali secondari. Questa diversità fra i risultati permette di identificare strategie diverse in funzione dell’elemento costruito. Anche A livello cronologico si osserva che ogni soluzione architettonica proviene da una profonda tradizione locale e difficilmente proviene da un sapere di nuova acquisizione se non al sorgere della manodopera specializzata. Questa ricerca ha permesso di conoscere e approfondire la tecnica della costruzione in terra cruda, seguendo un protocollo sperimentale che ha come obiettivo complementare lo studio dei processi costruttivi e l’approccio con pratiche di conservazione e restauro degli elementi prodotti con la terra cruda.
This PhD focuses the research on earth architecture in Late Prehistory (Neolithic and Bronze Age) from Near East. The need to work with one of the most abundant materials in the archaeological record such as earth transformed to mud-brick, pisé or tauf, among others, has led us to develop a complex analytical program that has been applied to 3 archaeological sites. Two of these are located in Syria (Tell Tell Halula and Tuqan) and one is located in Turkey ( Yumuktepe). All these sites have a different chronology, which allows the characterization and understanding of earth architecture technology, raw material acquisition process and technological knowledge related to structures coming from the public or private sphere. The introduction of archaeometric analysis in this field is a new research line where the absence of an stablished method of investigation does not allow performing comparative studies between the archaeological data and chronology. Therefore, in this study three sites were compared following the same methodological approach, which focuses on conducting chemical-physical analysis such as XRD, XRF, petrography and granulometry. These techniques are best used to characterize the materials and have been accompanied by other physical and mechanical tests such as porosity, determination and resistance determination through compression test. The structural nature of the material has validated the analysis in the following way. Samples coming from several domestic structures at Tell Halula (21 samples) are associated to a grill plan, constructed pits, ovens, niches, channelling and plasters. At Yumuktepe (17 samples) and Tell Tuqan (5 samples) mudbricks coming from many occupational phases have been studied with the aim to characterize mudbricks, floors and plasters from each period. The results allow the evaluation of the earth local acquisition hypothesis, specifically the catchment areas and the provisioning zones. The physical tests have determined differences in water content during the process of making bricks. All samples show calcite and quartz as the major mineral and others like feldspar and mica as secondary minerals. This diversity allowed the detection of differential strategies related to each constructed element. In a chronological level, it has also been shown that every architectural solution comes from a deep local tradition and hardly rises from newly acquired knowledge, until the emergence of the specialist craftsman. This work has also improved the knowledge of the ancient construction techniques identified by following an experimental protocol that has a complementary objective: to better understand construction processes and improve the conservation and restoration practices of items made in earth.

Varias técnicas de física nuclear tem sido aplicadas no estudo de artefatos arqueológicos e de arte contribuindo para seu restauro e preservação. A aplicação destas técnicas são indicadas por não serem destrutivas, preservando o material a ser analisado. Neste trabalho, propomos um procedimento para a investigação indireta da dureza de espadas antigas, por meio de técnicas não destrutivas. Com este proposito as técnicas PIXE, NRA, XRD e RBS se adequam ao nosso estudo de espadas antigas, especificamente uma espada Indiana (Damascena) e outra Japonesa (Wakizashi). Com a técnica PIXE esperávamos identificar os elementos presentes nas laminas das espadas e em suas empunhaduras. Na espada Indiana os elementos identificados foram: Cr, Mn, Fe, Ni, Cu, Zn e As. Para a espada Japonesa somente o elemento Fe foi identificado, mas com o auxílio da técnica RBS identificamos também, um filme fino de carbono na superfície da lamina, medindo 0; 75 _m de espessura. Nas empunhaduras foram identificados os elementos Cr, Fe, Cu e Au para a espada Indiana; Fe, Cu, As e Ag na peca Habaki e S, Cl, K, CA, Fe, As e Au na peca Fuchi, estas duas pecas fazem parte da empunhadura da espada Japonesa. A técnica XRD foi usada para verificarmos as estruturas cristalinas que se formam na superfície das laminas durante o processo de forja (variação de 6 temperatura e deformações plástica). Estas informações possibilitam inferir sobre a temperatura de forja e consequências da deformação plásticas. A fase cristalina da superfície das laminas foi identificada como ferro na forma cristalina cubica de corpo centrado. Nesta estrutura, ha a formação de pequenos cristais orientados (cristalitos), que apresentaram tamanho médio da ordem de 200 _A. Foi verificado que ha também uma fase amorfa do ferro na espada Japonesa, sugerindo que o processo de forja alcançou temperaturas menores quando comparada com a espada Indiana. A espada Damascena _e muito famosa pela dureza e ductibilidade apresentada por sua lamina. Um elemento que pode contribuir para estas caraterísticas e o nitrogênio, que pode ser identificado usando a técnica NRA, mais especificamente a reação 15N(p; _)12C. O nitrogênio poderia ser introduzido na lamina durante o processo de endurecimento da região de corte. Neste processo a lamina era resfriada em urina animal, composta principalmente por acido úrico (C5H4N4O3) e ureia (NH2)2CO. Não foi possível identificarmos a presença de nitrogênio dentro do nosso limite de detecção (acima de 0; 263(4)% em massa de nitrogênio, valor referenciado para a amostra padrão CRM-298).
A set of physical techniques have been applied to characterize archaeological and art artifacts and contribute to its preservation and restoration. The application of these techniques are indicated because they are non invasive methods, preserving the material to be analyzed. In this work, we propose a procedure to investigate indirectly the hardness of ancient swords, by nondestructive techniques. With this aim, we decided to apply the techniques PIXE, NRA, XRD and RBS in the study of ancient swords, specially Indian (Damascus blade) and a Japanese (Wakizashi) swords. With PIXE we identified the major compounds in the blades and in their grips. In the Indian blade were identified the following elements: Cr, Mn, Fe, Ni, Cu, Zn e As. In the Japanese only iron was identified, although, with RBS we could identified a thin _lm of carbon on its surface. The grips were also analyzed and the results indicated to Indian were: Cr, Fe, Cu and Au; and to Japanese: Fe, Cu, As e Ag in the peace Habaki, and S, Cl, K, CA, Fe, As e Au in the peace Fuchi, those pieces are part of the grip. The XRD technique was applied to verify the crystalline structure which were formed during the forging process (hammering and quenching). These information can help to understand more about the quenching and hammering process. The crystalline phase in the surface of the blade was identified as iron. The surface is composed by crystallites oriented with grain size in order to 200_A, oriented as the result of hammering process. Also there is an amorphous phase in the Japanese blade, suggesting that in the forje process the temperature achieved was lower when compared with the Indian sword. The Damascus blade is famous due its hardness and ductility. An element that can improve these characteristics is the nitrogen. Its determination is possible using NRA technique, more specially the reaction 15N(p; _)12C. The nitrogen could been insert in the blade during the edge hardness process (in this process the blade was quenched into animal urine that its main compound are uric acid (C5H4N4O3) and urea (NH2)2CO, or in a brine). It was not possible to identify the presence of nitrogen within our limit of quantification.

Neste trabalho foi investigado o efeito exercido por microambientes sobre a estabilidade química e fotoquímica de corantes. Em particular, estudaram-se os fatores responsáveis pelo aumento da estabilidade química e fotoquímica de índigo quando em interação com paligorsquita, que compõem o pigmento histórico Azul Maia, sobre o qual ainda havia controvérsias na literatura. Os corantes investigados foram índigo, dehidroíndigo, alizarina, purpurina, luteolina e β-caroteno; os microambientes foram proporcionados pelas argilas paligorsquita, sepiolita, montmorilonita, laponita e HDL de Al3+ e Mg2+ (3:1). Paligorsquita e a sepiolita são as únicas argilas que apresentam microporos em sua estrutura. As técnicas de caracterização empregadas neste trabalho foram: espectroscopia vibracional (Raman e absorção no infravermelho), espectroscopia de absorção no UV-VIS, difratometria de raios X, análise térmica (TG e DSC), CG-MS, HLPC-MS, medidas de área superficial por isoterma de adsorção de N2 e SEM. Duas técnicas com resolução temporal em escala de sub-picosegundos (absorção de transiente e infravermelho resolvido no tempo) foram utilizadas. O sistema índigo+paligorsquita corresponde à mistura dos dois sólidos, seguida de aquecimento, sendo que a partir de 70 °C a coloração da mistura adquire tonalidade esverdeada e também apresenta maior estabilidade química e fotoquímica. Essa estabilidade e também a alteração na cor aumentam com a temperatura de aquecimento da mistura e o intervalo considerado engloba as temperaturas de perda de água zeolítica (70 - 150 °C) e coordenada (170 - 280 °C) da estrutura da argila. Os resultados de espectroscopia vibracional e eletrônica dos simulantes de Azul Maia indicam que o índigo interage através de ligações de hidrogênio com as moléculas de água coordenada. Essa interação, entretanto, só é possível com a remoção da água zeolítica, o que ocorre a partir de 70 °C. Com aquecimento em temperaturas acima de 170 °C o comportamento do espectro eletrônico e vibracional se altera, indicando a formação direta de complexos com os metais presentes nas bordas internas dos microporos. Os resultados de espectroscopia Raman indicam que com a interação por ligação de hidrogênio a simetria molecular do índigo diminua. Os estudos por espectroscopia com resolução temporal mostraram que o índigo apresenta transferência de próton no estado excitado (ESIPT) de um dos amino grupos para a carbonila adjacente; após esta transferência, há a formação da espécie mono-enol a qual relaxa ao estado fundamental após 120 ps, através de intersecção cônica, o que explica a alta fotoestabilidade do corante. No caso da mistura aquecida a 130 °C os resultados, obtidos pela primeira vez para uma molécula imobilizada em argila, confirmam que o índigo encontra-se em um ambiente hidrofílico, considerando o tempo de vida de decaimento do estado excitado (3,0 ps), comparável ao do índigo carmim em solução aquosa (2,7 ps). O tempo de vida também é muito curto, comparado ao em solução de DMSO (120 ps) o que pode explicar a alta estabilidade do corante quando dentro do microcanal da argila. Finalmente, constatou-se que o dehidroíndigo não é responsável pela coloração de simulantes de Azul Maia, a qual resulta de alterações no espectro de absorção no visível do corante que ocorrem com a interação com a argila
In this work, the role played by the microenvironment on the chemical and photochemical stability of dyes was investigated. The factors responsible for the enhanced stability of indigo when interacting with palygorskite were detailed studied; the indigo and palygorskite system constitutes a simulant of Maya Blue, a historical pigment with properties which are controversially described in the literature. The dyes here investigated were indigo, dehydroindigo, alizarin, purpurin, luteolin and β-carotene; the microenvironment was provided by palygorskite, sepiolite, montmorillonite, laponite and a layered double hydroxide (Al3+ e Mg2+, 3:1). Palygorskite and sepiolite are the only clays with micropores in their structure. Several characterization techniques were employed, namely vibrational spectroscopy (Raman and infrared), UV-VIS electronic absorption spectroscopy, X-ray diffractometry, thermal analysis (TG and DSC), CG-MS, HPLC-MS, surface area and porosity determination (N2 isotherm adsorption) and scanning electron microscopy. Two sub-picosecond time resolved techniques (transient absorption and infrared absorption) were also used. The indigo+palygorskite system corresponds to the intimate mixture of both solids, followed by heating; from 70 °C the mixture attains a greenish hue and an enhanced chemical and photochemical stability. Both stability and color change increase with the heating temperature, which also leads to loss of zeolitic and coordinated water (70 to 150 °C and 170 to 280 °C, respectively). Vibrational and electronic spectroscopies indicate that, in the Maya Blue simulants, the dye interacts with the clay through hydrogen bonds with the coordinated water molecules. Such interaction, however, is only possible with the removal of the zeolitic water, which starts at 70 °C. At temperatures above 170 °C, both vibrational and electronic spectral profiles change, indicating that the interaction is now proceeding directly with the metals that are at the internal borders of the micropores. Results from Raman spectroscopy suggest that with the hydrogen bond and metal interaction a symmetry lowering occurs. Time resolved spectroscopy results show that indigo present an excited state intramolecular proton transfer from one of the NH to the adjacent carbonyl group, originating a mono-enol species, which decays to the ground state after 120 ps through a conical intersection. Such fast decay explains the high photochemical stability of indigo. In the case of the ind+paly mixture heated at 130 °C, the time resolved data obtained for the first time for a dye+clay system confirms that indigo is in a hydrophilic environment, taking into account the excited state lifetime (3.0 ps), comparable to indigo carmine in aqueous solution (2.7 ps). The excited state lifetime of indigo in the clay is also very short when compared to the experimental data for the dye in DMSO solution (120 ps), which is possibly an explanation for the dye high stability when inside the clay micropores. Finally, dehydroindigo was not found to be responsible for the color of Maya Blue simulants, which results from the spectral changes in the dye absorption spectrum originated by the interaction with the clay.

The Roman villa of Frielas is an archaeological site from 3rd – 6 th century AD located in Loures, Portugal. The villa is on excavation since 1997. The site is an area of 3500 m2 . The area still under excavation corresponds to the villa's urban pars. The villa has two construction phases, the first phase is very limited with structural evidence and mostly destroyed during the construction of 2nd phase. The 2nd phase has evidence of architectural features with functionality mainly, some compartments surrounding the peristyle with portico and mosaic floor passages. And its abandonment occurred at the beginning of the 7th century A.D. The abandonment phase has no remarkable architectural features, except some unfinished walls or destruction of earlier phases. A total of eighteen mortar samples were collected from the different structures of the villa with different functional uses (render, filler, and floor) and analyzed by a multi-analytical approach by means of Optical Microscopy, (Stereo zoom and Petrographic microscope), X ray Diffraction (XRD), Variable Pressure Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (VP-SEM-EDS), Thermogravimetric analysis (TGA DTG), Acid attack and Granulometric analysis. The results revealed a similar composition of calcitic aerial binder, while differences in aggregates allowed to establish 4 groups. Raw materials are local and within a radius of 5Km. There was no prominent variation that can suggest a different chronology between the four groups. Though, it is assumed that there might be some renovation, restoration, or partial rebuilding that occurred in the same period. In terms of production technology, it is evident that the Vitruvius rules were not followed; R E S U M O: Estudo de argamassas históricas da villa romana de Frielas (Loures, Portugal) A villa romana de Frielas é um sítio arqueológico do século III ao IV DC localizado em Loures, Portugal. A villa romana está em escavação desde 1997. O local tem uma área de 3500 m2 . A área ainda em escavação corresponde à área urbana da villa. Esta apresenta duas fases de construção sendo que a primeira fase é muito limitada com poucas evidências estruturais e/ou destruídas durante a construção da 2ª fase. A 2ª fase apresenta evidências de características arquitetónicas com funcionalidade principalmente, alguns compartimentos circundando o peristilo com passagens de pórtico e piso de mosaico. E seu abandono ocorreu no início do século 7 d.C. A fase de abandono não tem características arquitetônicas notáveis, exceto algumas paredes inacabadas ou destruição de fases anteriores. Um total de dezoito amostras de argamassas com usos funcionais distintos (reboco, enchimento e assentamento) foram recolhidas, em diferentes estruturas da villa, e analisadas por uma abordagem multi-analítica compreendendo a Microscopia Ótica (estereomicroscopia e petrografia), a Difração de raios X (DRX), a Microscopia Eletrónica de Varrimento – Espectroscopia de Energia Dispersiva de raios X (MEV-EDS), a Análise Termogravimétrica (ATG-DTG), o Ataque Ácido e a Análise Granulométrica. Os resultados revelaram que as argamassas estudadas apresentam uma composição semelhante, ligante de cal calcítica, enquanto que as diferenças nos agregados permitiram estabelecer 4 grupos. As matérias-primas são locais e num raio de 5km. Não se verificaram variações significativas que possam sugerir uma cronologia diferente entre os quatro grupos. Porém, presume-se que pode ter havido alguma renovação, restauro ou reconstrução parcial ocorrida no mesmo período. Em termos de tecnologia de produção, é evidente que as regras de Vitruvius não foram seguidas.

The Caucasus is a land corridor between the Black and Caspian seas, linking Africa to Northern Eurasia, and is considered a migratory route for Neanderthals and Anatomically Modern Humans (AMH). Numerous cave sites in Armenia, Azerbaijan, Georgia and southwestern Russia indicate that Neanderthals and AMH occupied the region, but poor chronological control meant that the precise timing of the occupations was unknown. This work involved identifying and geochemically characterising volcanic ash layers (tephra) in archaeological cave and open air sites spanning approximately 125 ka to 30 ka to generate a tephrostratigraphic framework. This framework was used to correlate the sites and assess the synchronicity of Neanderthal and AMH occupation across the region. Tephra investigations were also carried out on a core (M72/5-25-GC1) from the southeast Black Sea (that spans the last ~ 60 ka), with the aim of linking the archaeological sites to this palaeoenvironmental archive, to investigate the impact changes in climate had on the archaeology in the region. Eleven of the archaeological sites investigated (Gubs rock shelter and Weasel Cave in Russia; Ortvale Klde, Ortvale Cave, Sakajia and Undo Cave in Georgia; Aghitue 3, Lusakert 1, Fantan and Kagasi in Armenia; and Azokh Cave in Azerbaijan) had tephra, 30 cryptotephras and 8 visible layers, preserved. Twenty-two tephra layers were identified in the Black Sea core, with distinct periods of frequent volcanic activity separated by long periods, up to 9 ka, of seemingly volcanic quiescence in the region. The glass chemistry of the tephra found in the archaeological sites and the core, determined using a wavelength-dispersive electron microprobe, was used to characterise and correlate the units between the sedimentary sequences. Although some widespread tephra from the major Mediterranean sources (3.6 ka Minoan eruption from Santorini, Greece and the ~39 ka Campanian Ignimbrite super eruption from Campi Flegrei, Italy) were identified in the Black Sea core, none of the archaeological sites contained Mediterranean tephra. Most of the tephra layers in the archaeological sites investigated and the Black Sea core are from sources in the Caucasus and Turkey. The limited information on the volcanic history and compositional data of these sources in the region does not allow most of the units to be correlated to particular eruptions or volcanoes. However, some of the cryptotephra units have been correlated to eruptions from Nemrut, Acigöl and Erciyes Dagi volcanoes in Turkey. Unfortunately, there are no tephra layers that are common to the Black Sea core and any of the archaeological sites, prohibiting direct correlation of the sites to this detailed palaeoenvironmental record. However, the ~30 ka Nemrut Formation (NF) eruption from Nemrut volcano, Turkey, is found in the Lake Van palaeoenvironmental record and in two of the archaeological sites. This allows the archaeological sites to be correlated to each other and palaeoclimate information can also be imported into these sites. More detailed characterisation of the proximal deposits may allow more units to be correlated to eruptions and will enable these distal records to be used to further constrain the tempo of explosive volcanic activity in the region. A few compositionally distinct tephra layers were found and a suite of new radiocarbon dates were obtained at various sites, allowing archaeological occupations to be dated and the synchronicity between sites to be assessed. A distinct rhyolitic tephra correlates a layer with an Upper Palaeolithic stone technology, associated with AMH, in Azokh Cave (Azerbaijan) to a layer in Sakajia cave (Georgia) that contains Neanderthal remains. This is clear evidence that AMH and Neanderthals were in the region (within 600 km) at the same time. Other sites have also been correlated with tephra. A dacitic tephra correlates a unit with an Upper Palaeolithic lithic and bone tool techno-complex in Ortvale Klde (Georgia) to a unit with a Middle Palaeolithic lithic assemblage in Lusakert 1 (Armenia). The Middle Paleolithic tool assemblage in Lusakert 1 is clearly different from the Upper Paleolithic assemblage that is clearly associated with AMH in Ortvale Klde, but it is not clear whether the other assemblage is associated with Neanderthals, archaic modern humans or AMH. This correlation between different lithic assemblages clearly indicates that there were different groups, with different technologies, occupying the region at the same time. The NF tephra is also found shallower in the sequences at both Lusakert 1 and Ortvale Klde. This time marker shows that the Middle Paleolithic assemblage is still being used in Lusakert 1 at ~30 ka, indicating that a less diverse stone techno-complex was used for a prolonged period of time in central Armenia. There does not appear to be any direct relationship between occupation in the region and the climate at the time, implying that this had little effect on the archaeological story in the region. A new radiocarbon based age model that combines new dates with published data for the sites within the Caucasus shows temporal overlap between AMH and Neanderthals in the region. This confirms the tephra correlations and clearly indicates both species co-existed in the Caucasus. The new radiocarbon data also suggest that AMH arrived in the region earlier than previously thought, at ~50-44 ka cal BP. The arrival of AMH in the Caucasus is now temporally similar to other early AMH sites in northern Eurasia.

In the archaeological record the ceramic remnants are among the strongest materials since their origin. The pottery study is therefore very important for archaeology for many different reasons. First of all the morphological features of the vase shapes, their decoration as well as the production technology are usually a peculiar element of the community that produced them. These elements make ceramic a craft-made expression and an artistic expression of a certain culture and the ’key fossil‘. Pottery is also one of the most significant indicators to measure the technological development of a society in a particular period of time. Furthermore pottery gives relevant information about both the contacts and the social relations, which occurred between neighbouring and far away countries, and trades between different populations. Through archaeological and archaeometric analysis of vase shards, this project aimed to highlight the contacts, the social relations and the trades occurred between the protohistorical populations from the north-east of Italy, particularly the Veneto region, and other populations settled in the Italian peninsula or up north the Alps. Secondly, the study was addressed to investigate the production technology adopted for manufacturing these artefacts and to characterize in detail the compositional variability of the pottery in terms of chemistry and petrography. Where possible, in addition to the archaeological finds, a series of clays and sands sampled from potential provenance sites were studied. The research were carried out through optical microscopy (petrographic microstructural and textural analysis) and image analysis on scanning electron microscopy (image and elemental maps), the mineral assemblages were gained by X-ray diffraction (XRD), geochemical analysis by X-ray fluorescence (XRF) and multivariate statistical analysis. Three case studies were selected, each involving different regions and a wide chronological interval, in order to develop the research project: a) The site of Castel de Pedena (Belluno, Italy), dated between the end of the Old Bronze age and the end of the Late Bronze age (XVIII-X Century b.C.). Particular interest was here addressed to some jars found in the site, typical of the Alpine Luco/Laugen-Meluno/Melaun culture. Although no ceramic trade could be identified for these vases with the regions where the Luco/Laugen culture was well attested -Italian South Tyrol and Trentino, Austrian East Tyrol, Liechtenstein and Swiss Grisons regions- a so high similarity in the shapes of vessels and in the production technology proves the existence of intensive contacts. Furthermore, the study of the pottery assemblage of Castel de Pedena allowed to delineate the evolution of the production technology from the Recent Bronze Age to the first Iron. b) The flared rim and flattened lip ceramics (FRFL pottery), a peculiar type of vase that spread across the Friuli Venetia Giulia region (north-east of Italy), between the final Bronze Age and the beginning of the Iron Age, but found also in few sites of the neighboring Veneto region. The archaeometric analyses of FRFL pottery coming from three sites of Veneto (Concordia Sagittaria, Padova, Castion d’Erbè) revealed that they had high similarity in the preparation process since they were realised using similar recipes in terms of abundance and type of temper. Inclusions were represented mostly by concretions of speleothems, a very peculiar type of rock. Moreover, comparison with the local Venetian products indicated that the FRFL pottery were compositionally distinct. On contrast they showed great similarity with FRFL shards coming from sites of the Friuli Venetia Giulia region. The presence of speleothems related this pottery to the Friuli Venetia Giulia, a karsic region with presence of more of seven-thousand caves, and it suggested that they were transported in Veneto for some specific product trade. c) The site of Fondo Paviani (Verona, Italy), dated between the end of the Middle Bronze age and the beginning of the Late Bronze age (XIV-XII Century b.C.). During the Recent Bronze Age the common use of produce coarse pottery with macroscopically similar pastes spread in all the ’Palafitticolo Terramaricola‘ culture sites. Since in the coeval level of the site of Castel de Pedena specimens typical of the plain culture were found, some specimens from Fondo Paviani were selected with the intention to compare them with macroscopically similar shards from Castel de Pedena, dated at the same age. This third ’case study‘ concerned a small number of potsherds coming from the site of Fondo Paviani (Verona, Italy). It must be consider a preliminary study and not statistically representative of the real context of the site. For the same reason it was not possible to make any general correlation between the pottery productions of Fondo Paviani and Castel de Pedena.
I materiali fittili sono fra i prodotti più resistenti nel record archeologico a partire dalla loro invenzione nell’antico Neolitico. Per questo il loro studio è di grande importanza per l’archeologia sotto molteplici aspetti. In particolare le forme vascolari, le loro decorazioni e la tecnologia di produzione sono normalmente peculiari delle comunità che le hanno prodotte. Questi elementi fanno della ceramica espressione artigianale, e nelle fasi più recenti anche artistica, e tecnologica di una cultura, qualificando tale prodotto come ‘fossile guida’ d’eccellenza e come uno degli indicatori parziali più sensibili del livello di organizzazione del lavoro raggiunto da una data società in un determinato periodo. La ceramica inoltre fornisce importanti informazioni sui rapporti sia di integrazione sociale tra popolazioni confinanti o anche ad ampio raggio, sia indicando rapporti commerciali tra gruppi diversi. Attraverso l’analisi archeologica e archeometrica di frammenti vascolari, col presente progetto si è cercato di fare luce principalmente sui rapporti di interazione sociale, di scambio o commerciali tra le popolazioni protostoriche dell’Italia settentrionale -con particolare riferimento alla zona veneta- e le popolazioni coeve della penisola e d’oltralpe. A tal fine si è ritenuta necessaria la distinzione tra manufatti realmente di importazione e manufatti che imitano modelli di provenienza alloctona, l’individuazione dei centri produttori di tali manufatti, l’identificazione delle vie percorse dai traffici e la definizione delle relazioni tra le culture locali. Non si è voluto tralasciare inoltre la comprensione e la ricostruzione della tecnologia ceramica adottata, della tipologia dei materiali utilizzati e del luogo di approvvigionamento delle materie prime. Dove possibile al lavoro sui materiali fittili è stata associata l’analisi di campioni di argille o sabbie provenienti da potenziali aree di approvvigionamento preceduta dallo studio dettagliato della geologia dell’area di interesse. Analisi petrografiche e microstrutturali sono state condotte attraverso osservazione al microscopio ottico ed elettronico (analisi di immagine). Lo studio delle fasi mineralogiche presenti nei campioni ceramici è stato condotto attraverso analisi diffrattometrica dei raggi X su polveri mentre la composizione chimica è stata ottenuta per fluorescenza dei raggi X sui cui risultati sono state condotte analisi statistiche multivariate. In particolare sono stati presi in considerazione tre casi studio: a) Il sito d’altura di Castel de Pedena (Belluno), datato tra il tardo Bronzo antico e il tardo Bronzo finale/prima età del Ferro. Durante gli scavi sono stati raccolti numerosi reperti ceramici vascolari alcuni dei quali riconducibili alla cultura alpine Luco/Laugen-Meluno/Melaun. Sebbene non sia stata riscontrata nessuna testimonianza di rapporti commerciali riguardanti questa tipologia vascolare con le aree pertinenti -il Trentino, l’Alto-Adige, il Tirolo Orientale e la Bassa Engadina- la forte somiglianza tra i reperti rinvenuti presso sito e il cosiddetto boccale tipo Luco sembrerebbe provare intensi contatti tra le due culture. Infine, lo studio dell’intero repertorio ceramico proveniente da Castel de Pedena ha permesso di ricostruire l’evoluzione della tecnologia di produzione della ceramica dall’età del Bronzo Recente fino alla prima età del Ferro. b) La ceramica a orlo svasato superiormente appiattito (qui chiamata FRFL pottery) si diffusa nel Friuli Venezia Giulia (Italia nord-orientale) tra la fine dell’età del Bronzo Finale e la prima età del Ferro. Questa tipologia vascolare trova però confronti anche in reperti provenienti da alcuni abitati coevi di area veneta. Le analisi archeometriche di alcuni reperti di vasi provenienti dai siti veneti di Padova, Concordia Sagittaria e Castion d’Erbé hanno rivelato che gli impasti dei campioni sono simili tra loro sia per l’abbondanza di inclusi sia nella peculiare scelta della tipologia litica adottata: sono stati fatti utilizzando frammenti di concrezioni di grotta (speleotemi). Inoltri il confronto con frammenti di vasi di tipologie tipiche venete, e quindi di probabile origine locale, ha dimostrato che questi vasi sono composizionalmente distinti mentre hanno grande somiglianza con ceramiche ‘FRFL’ di provenienza friulana e giuliana. La presenza di speleo temi le mette in relazione con la regione della Venezia Giulia, un’area carsica dove si conoscono oltre settemila grotte. Sembrerebbe quindi che fossero state trasportate in Veneto, probabilmente per scopi legati al commercio di qualche prodotto specifico. c) I reperti provenienti dal sito arginato di Fondo Paviani (Legnago, Verona), datato tra la fine dell’età del Bronzo Medio e l’inizio del Bronzo finale (XIV-XII secolo a.C.). Il sito arginato di Fondo Paviani (Verona) si data tra la fine dell’età del Bronz Medio e l’inizio del Bronzo Finale. Durante l’età del Bronzo Recente è stato osservata nell’area ascrivibile alla cultura ‘Palafitticolo Terramaricola’ l’abitudine comune di produrre ceramica vascolare grezza caratterizzata da impasti macroscopicamente simili. Materiali simili, ascrivibili all’età del Bronzo recente, sono stati trovati anche presso l’abitato di Castel de Pedena. Questo ha indotto a studiare un piccolo numero di questi reperti provenienti da Fondo Paviani con l’intenzione di confrontarli con i coevi materiali di Castel de Pedena. Dato l’esiguo numero di campioni, questo ultimo caso studio è da considerarsi uno lavoro preliminare i cui risultati non sono statisticamente rappresentativi del contesto reale del sito. Per lo stesso motivo non è stato possibile trovare alcuna correlazione coi reperti di Castel de Pedena, e con la tecnologia di produzione adottata in antichità presso il sito.

Neste projeto foram determinadas as concentrações elementares de Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn por meio da análise por ativação com nêutrons instrumental (INAA) em 60 amostras de sedimento do sítio arqueológico Lapa Grande de Taquaraçu, localizado no Estado de Minas Gerais. As amostras foram cedidas pelo Prof. Dr. Astolfo Gomes de Mello Araujo do Museu de Arqueologia e Etnologia da USP (MAE-USP). Este sítio é um abrigo paleoíndio rochoso localizado próximo ao carste de Lagoa Santa, com características que poderiam ser usadas para testar o modelo de abandono do carste durante o Holoceno Médio relacionado ao aumento da seca. Os resultados das concentrações elementares, interpretados por métodos estatísticos multivariados, mostraram a formação de três grupos composicionais distintos e bem definidos. Foi realizado, também, o estudo de seleção de variáveis por meio da análise de Procrustes. Com o propósito de estudar a composição mineralógica, foram selecionadas 8 amostras, as quais foram analisadas por difração de raios X. Os resultados indicaram que há distinção na estrutura cristalina entre as amostras dos três grupos composicionais, sendo quartzo, calcita, dolomita e mica as principais fases cristalinas.
In this project the elemental concentrations of Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn were determined by instrumental neutron activation analysis (INAA) in 60 sediment samples from Lapa Grande de Taquaraçu archaeological site, located in MG State. The samples were provided by Dr. Astolfo Gomes de Mello Araujo from the Museum of Archaeology and Ethnology, University of São Paulo. This site is a palaeoindian rockshelter located near Lagoa Santa karst with characteristics which could be used to test karst abandonment model during the Middle Holocene related to dry conditions. The results of elemental concentrations, interpreted by multivariate statistical analysis, showed the formation of three different compositional and well-defined groups. The variable selection study by means of Procrusts analysis was also carried out. X-ray diffraction (XRD) analyses were also performed in 8 samples to study their mineralogical composition and they showed that there are distinctions in crystalline structure between the samples of the three elemental compositional groups, being quartz, calcite, dolomite and mica the main crystalline phases present in the samples.

Moving away from the highly regionalised and constrained purely humanistic and empirical studies of hillfort location and morphology, this study is a multi-regional GIS-based analysis of the form and siting of several groups of hillforts across Britain. Hillforts in Dartmoor, Aberdeenshire, The Gower and Warminster are assessed, four regions that are topographically diverse. The highly varied topography of these regions also tests the GIS-basis of this study, another important intrinsic aspect of this novel research. GIS-based analysis has never before been applied to a study of hillfort location and morphology to this degree and, as with any innovative methodology its worth has to be tested and assessed. The thesis demonstrates that GIS-based analysis, when combined with field visits, provides a fundamental insight into the possible influences of hillfort location and morphology, which fieldwork alone will never be able to do. The GIS-based analysis developed here focuses largely upon examining degrees of movement and visibility. Unlike other GIS-based analyses of movement and visibility this integrates the two to examine visual pathways across landscapes to further investigate the visual qualities of hillforts within the various test areas. The study demonstrates that GIS-based analysis when combined with fieldwork can be affectively applied to qualitative based questions surrounding hillfort location and morphology. The overall results of this analysis had some relatively predictable results whilst there were some very surprising cases. A large number of entrances were placed within the most accessible area, however in the case of Battlesbury there was evidence for the complete disregard to accessibility within the orientation of its northwestern entrance. There were also numerous examples of the placement of a site's most prominent morphological components in correlation with the blind pathways. In these cases sites were orientated to encourage an element of surprise upon the approaching travellers.

Nul autre vase en céramique n'aura mieux que le dolium rendu compte de la démesure romaine. C'est par ces mots que débute la présente synthèse qui porte sur le dolium en Gaule Narbonnaise à l'époque romaine.D'abord importée par les Grecs en Italie dans le courant du VIIIe s. av. J.-C., cette grande jarre de stockage en terre cuite va peu à peu conquérir l'ensemble de la Méditerranée nord-occidentale. Parce qu'il constitue un conteneur parfaitement adapté au climat chaud du pourtour méditerranéen, il devient dans le courant du IIe s. av. J.-C. le symbole de la viticulture et de l'oléiculture intensive, et ce au moins jusqu'au IIIe s. ap. J.-C.L'archéologie a longtemps délaissé ce matériel lourd et souvent informe qui jonche pourtant le sol des anciens chais et celliers à dolia des exploitations agricoles antiques. À travers le cas particulier de la Gaule Narbonnaise, le présent travail se propose de réévaluer la place qu'a pu jouer ce conteneur dans le développement économique de cette province, entre le Ier s. av. J.-C. et le IIIe s. ap. J.-C. Utilisant les méthodes de l'archéologie classique, cette étude s'inscrit aussi dans une perspective pluridisciplinaire destinée à mettre en synergie les données archéologiques, archéométriques, épigraphiques et anthropologiques.L'ensemble de la documentation rassemblée constitue une synthèse inédite des connaissances sur le thème du dolium, depuis sa fabrication jusqu'à son utilisation, qui vise à mettre en évidence les modalités du déploiement de ce formidable outil au service du développement économique impérial
The dolium as no other pottery represents the roman excessiveness. By these words begins the present synthesis that deals with dolium in Gallia Narbonensis.First introduced by Greeks in Italy during the VIIIth s. B.C., this large jar in terracotta will gradually conquer all northwest Mediterranean. As it is perfectly adapted to warm climate of Mediterranean periphery, it became during the IIth s. B.C. the wine and oil intensive production's symbol, at least until the IIIth s. A.D.Archaeology has for a long time neglected this heavy materiel whereas it strews the floor of antics cave and cellar. Through the example of Gallia Narbonnensis, this study aims at reassessing the position of this container in the economic expansion of this province between the Ith s. B.C. and the IIIth s. A.D. Using classical archaeological method, this research includes also a multidisciplinary viewpoint intended to synergise archaeological, archaeometrical, epigraphical and anthropological data.All this documentation constitutes an unprecedented synthesis on dolium, from its manufacturing to its use. The final goal is to bring out the model of deployment of this great instrument, which is assigned to the imperial economic development

This project represents the first comprehensive study applying molecular and genetic methods to study historical contexts such as migration and trade based on human parasites. Using specially developed techniques, the study focused on parasites with minor symptoms which allowed the infected person to go about their daily business. The combination of state of the art techniques in archaeology, molecular methods and phylogenetic analysis enabled us to develop a novel powerful tool to study historic events. Diseases have a considerable impact on societies. Various publications indicate that human intestinal parasites are commonly found in a variety of archaeological contexts, including latrines, graves and mummies. These parasites can be detected by microscopy which focuses the work on samples which do close association to humans; widespread prevalence and the possibility for reliable microscopic diagnostics suggest that these parasites are an attractive study system for human activities. Infectious diseases have a much short generation time which offers greater opportunity to track historical events at higher resolution. Looking at a range of human parasites, their different life-cycles allowed insight into various aspects of human culture, comparing different origins of the samples allows an estimation of the epidemiological burden of ancient populations. Application of a parallel sequencing approach (MiSeq) enabled building a comprehensive database of sequences from various archaeological sites dating as far back as 3630 BCE. Indepth phylogenetic analysis reveals patterns in the genetic signatures of both coding and non-coding genetic regions, taking various levels of selective pressure into account. This project has produced the oldest pathogen sequence and the most comprehensive database of ancient pathogen sequences.

Ce travail de thèse a pour objectif d’étudier l’emploi des motifs géométriques, végétaux ou empruntés à l’architecture, dans le décor peint des monuments funéraires de Macédoine antique. Il s’agit d’une approche intégrale qui est effectuée à travers la documentation et l’analyse stylistique, technique et physico-chimique des motifs tels qu’ils apparaissent dans un riche corpus de soixante-huit monuments datés de l’époque hellénistique et le début de l’époque romaine. La thèse est organisée en trois parties. La première partie présente la documentation des motifs rencontrés, leur occurrence dans les monuments avec des observations sur le rendu, les combinaisons chromatiques et les pigments employés. Cette partie comprend une étude comparative des motifs dans l’art de l’antiquité en Grèce et ailleurs, et des commentaires sur l’origine et le symbolisme des motifs et leur transposition de la réalité ou de l’architecture dans la peinture.La deuxième partie concerne l’étude archéométrique des matériaux picturaux employés. Des prélèvements ponctuels ont été effectués sur le décor de vingt tombes et analysés au moyen de méthodes photographiques et physico-chimiques, in situ et en laboratoire. La présentation de la méthodologie et les résultats obtenus au cours de cette étude se fait de façon analytique et systématique. La troisième partie présente un catalogue illustré des tombes peintes de Macédoine classé selon leur type architectural, comprenant les données de fouille, la description du décor peint des surfaces pariétales et de l’aménagement intérieur et des informations concernant l’architecture et les matériaux picturaux. Les différents types de motifs ornementaux rencontrés et les types de moulures sur lesquelles ils sont réalisés sont présentés dans un lexique illustré
The objective of this thesis is the study of the architectural, geometric and vegetal motifs that decorate the funerary monuments of Macedonia. An integral approach has been applied, combining detailed documentation with the stylistic, technical and physicochemical analysis of the motifs, as they appear in a rich corpus of sixty-eight monuments that date in the Hellenistic and early Roman period. The thesis is organised in three parts. The first part provides the documentation of the motifs, their occurrence in the monuments, along with observations on their design, the chromatic combinations and the pigments employed. This part includes a comparative study of the motifs in the art of ancient Greece and elsewhere, as well as commentaries on their origin and symbolism or the transformation from real objects or architectural elements into painted motifs. The second part concerns the archaeometrical study of the painting materials used. Samples from twenty tombs have been collected and analysed by means of photographical and physicochemical methods, both in situ and in the laboratory. The methodology and the results obtained during this study are presented systematically and in detail. The third part consists of an illustrated catalogue of the painted tombs of Macedonia, according to their architectural structure, which comprises the excavation data, the description of the painted decoration on the walls surface and on the funerary pieces of furniture as well as information on the architecture and the painting materials. The different ornamental motifs and types of moulding on which they are painted, are presented in an illustrated glossary of terms

L’espace lorrain a connu, au cours des XIXe et XXe s., une intense activité sidérurgique reposant sur la réduction d’un minerai sédimentaire, la Minette lorraine. Paradoxalement, on a longtemps considéré qu’aucune activité de production liée à l’exploitation de ce minerai n’avait pris place dans cette région avant l’époque contemporaine. Un programme de recherche initié il y a 25 ans a par ailleurs totalement renouvelé la perception de l’histoire sidérurgique de cet espace. Les activités de production s’y sont déroulées de manière sporadique dès les âges du Fer, avant de prendre de l’ampleur au cours de la période médiévale. Les recherches menées permettent une première appréhension de l’évolution des modes de production du fer en Lorraine à différentes époques, mises en perspective dans leur contexte européen. Toutefois, les modalités de distribution du métal produit restent largement méconnues, du fait de l’indigence relative des sources historiques à cet égard. Une première perception des circuits de distribution du fer se développant au sein de l’espace lorrain est exposée dans ce mémoire, contribuant à l’appréhension des usages du fer à différentes époques.Une méthodologie développée récemment par le Laboratoire Métallurgies et Cultures et le Laboratoire Archéomatériaux et Prévision de l’Altération, reposant sur la caractérisation chimique des déchets associés à la réduction du minerai et des inclusions présentes dans les produits sidérurgiques, a été employée dans ce but. Ce travail interdisciplinaire propose par ailleurs de nouveaux développements en termes de traitement statistique multivarié de l’information chimique, contribuant ainsi à répondre aux problématiques développées.Un référentiel géochimique, constitué d’une base de données préexistante et d’informations nouvelles acquises à l’occasion de prospections archéologiques, offre une perception nouvelle de la diversité chimique caractérisant les activités sidérurgiques anciennes au sein de l’espace lorrain et de ses marges. Des ensembles géochimiques de production ont ainsi été mis en évidence. Plusieurs contextes de consommation ont ensuite été considérés, offrant un éclairage sur les circuits de distribution du fer aux époques anciennes en Lorraine. Une démarche statistique, reposant sur l’emploi d’analyses descriptives et de modèles prédictifs, a été appliquée en ce sens, après avoir été éprouvée par l’étude d’ateliers sidérurgiques pour lesquels l’utilisation d’un minerai en particulier est assurée par le contexte archéologique.Les résultats obtenus permettent de préciser, parfois à l’encontre des hypothèses formulées au préalable, les pratiques d’échange du fer à différentes époques, en regard de nos connaissances quant aux modes de production sidérurgiques. Des discussions portant sur le rôle joué par le travail du fer au sein des sociétés anciennes sont initiées à la lumière des informations nouvellement acquises
Lorraine was, during the 19th and 20th c., one of the most important ironmaking areas worldwide, relying on the use of a sedimentary ore, the Minette lorraine. Paradoxically, it has long been thought that no iron was produced using this ore before the modern era. A research program initiated 25 years ago totally renewed our perception of its metallurgical history. Production activities were indeed sporadically performed since the Iron Age, before drastically increasing during medieval times. Research performed allows a first apprehension of the ironmaking activities’ forms in Lorraine and their evolution through successive periods, put into perspective in the European context. Iron trade and circulation remain however largely unknown, due to the lack of historical sources. A first insight of the trade networks relative to iron products extending throughout Lorraine and its fringes is exposed in this thesis, contributing to the perception of the use of iron in different periods.A methodology recently developed by the Laboratoire Métallurgies et Cultures and Laboratoire Archéomatériaux et Prévision de l’Altération, relying on the chemical characterization of smelting slags and slag inclusions entrapped in iron products, was employed to that purpose. This interdisciplinary work also offers new developments in the multivariate statistical treatment of chemical information, and contributes to answering the issues raised at the beginning of this work.A geochemical reference set, comprised of a pre-existing database and new information gathered on archaeological surveys performed during this work, was set up. It provides a new perception of the chemical diversity characterizing iron smelting activities within Lorraine and its fringes. Geochemical production sets were emphasized in doing so. Several iron consumption contexts were then considered, offering the possibility of shedding light on iron spreading networks during ancient times in Lorraine. A statistical approach, relying on the use of both descriptive statistical analyses and predictive modelling, was applied to that purpose. It was beforehand tested by studies performed on workshops for which the use of a given ore is attested by archaeological records.Results allow enlightening, sometimes against formerly formulated hypotheses, the practices in terms of the iron’s trade through different periods, facing our current knowledge about iron production modes. Benefiting from newly gathered information, discussions about the role played by ironworking activities among ancient societies are initiated

En este trabajo se presentan los resultados del estudio de la caracterización arqueométrica de un conjunto de cerámicas de cocina tardoantiguas, datadas entre los siglos V y VIII. La piezas seleccionadas proceden de yacimientos del noreste de la península ibérica, concretamente el ager de Barcino y de Iluro. De esta forma, se han seleccionado materiales de siete yacimientos: tres en el Vallès Occidental, Can Gambús, Horts de Can Torras, Plaça Major de Castellar del Vallès; uno en el Vallès Oriental, Ca l'Estrada y tres en el Maresme, Torre Llauder, Can Modolell e Iluro, el único contexto urbano. A partir del análisis arqueométrico se pueden definir las URCPs, puesto que todos los individuos provienen de centros receptores. Con ello, se pueden establecer hipótesis de proveniencia de cada una de estas URCPs, diferenciando en un primer nivel entre producciones autóctonas e importaciones. Dentro de estas producciones autóctonas, se procurará diferencian entre las URCPs del Vallès y las del Maresme. Con esto, se pretenden proponer posibles núcleos de producción, así como su difusión por el territorio a través de posibles intercambios comerciales regionales entre las URCPs del Vallès y las del Maresme. Estos materiales se han caracterizado arqueométricamente para poder identificar la composición de las cerámicas y a partir de aquí, poder establecer hipótesis de proveniencia. Para ello se han realizado, análisis químicos por fluorescencia de rayos X (FRX) y el tratamiento estadístico de sus resultados, análisis mineralógico por difracción de rayos X (DRX)y análisis petrográficos con la observación de láminas delgadas en el microscopio óptico (MO). Así mismo, dada la complejidad de los resultados, con fuertes similitudes entre sí, se ha realizado también un análisis de arcillas. Para ello se recogieron seis muestras de arcilla de distintos puntos del Vallès Occidental, siguiendo las directrices de proximidad geográfica a los yacimientos y diversidad geológica. La combinación de estos análisis ha permitido la caracterización de las cerámicas. En primer lugar, se aprecia un predominio de la composición granítica de las cerámicas, así como frecuentes inclusiones sedimentarias. De esta forma, se pueden apreciar dos grupos, uno formado por composición granítica y otro granítico con aportaciones metamórficas. Esta composición implica fuertes similitudes entre los individuos y entre los grupos definidos, por lo que la diferenciación de sub-grupos viene dada mayormente por criterios texturales. Esta composición granítica y metamórfica se corresponde con la geoquímica de la zona donde se sitúan los yacimientos muestreados, identificándose muy raramente inclusiones y pastas alógenas que se limitan al yacimiento urbano y costero de Iluro. De esta forma, la mayor parte de las URCPs definidas corresponden a producciones locales o regionales. Se han podido distinguir fábricas regionales, tanto del Vallès como del Maresme, así como algunas fábricas locales, propias de un yacimiento en concreto. A pesar de esta evidencia, la difusión regional de la cerámica es escasa, se puede observar un ligero intercambio regional, con algunos individuos de fábricas del Maresme hallados en el Vallès y viceversa.
This work presents the archaeometric study of Late Roman Cooking ware from the ager of Barcino and Iluro, located on the North-East of the Iberian Peninsula. Samples from seven settlements have been selected: three from Vallès Occidental, Can Gambús, Horts de Can Torras, Plaça Major de Castellar del Vallès; one in Vallès Oriental, Ca l'Estrada and three from Maresme, Torre Llauder, Can Modolell and Iluro, the only urban context. The archaeometric analysis allows us to define URCPs that permit to establish provenance hypothesis, distinguishing between imports and autochthonous productions and between Vallès and Maresme productions. In this way, there can be proposed some pottery production centers and their diffusion in short distance trade between both regions. This characterization has been done through the combination of chemical analysis, performed with X-Ray fluorescence (XRF), mineralogical analysis, carried out with X-Ray diffraction (XRD) and petrographic determination with thin sections observed on optical microscopy (OM). Besides, due to the similarity of the samples, clay analysis has been added, with six samples from different geological areas of Vallès Occidental. The results of these analyses reveal a predominance of granitic composition. There can be observed to clear tendencies, one with granitic composition and a second one granitic with metamorphic contribution. The similarity with these groups and samples means that the sub-groups depend on textural criteria. The compositional results match with geochemistry of the area of the sampled settlements. Outside inclusions and pastes are rare and limited to the urban settlement of Iluro. So that, defined URCPs belongs mainly to local or regional productions, with the identification of Vallès fabrics and Maresme fabrics, as well as some local productions belonging to concrete settlements. Although this pottery diffusion is very scarce, some short distance trade can be observed, with some Maresme pieces found in Vallès and vice versa.

Objetivou-se, com este trabalho, estudar os métodos hierárquicos de análise de agrupamentos (ligação simples, ligação completa, ligação média, centróide e de Ward com base nas distâncias Euclidiana, Euclidiana ao quadrado, Manhattan e Mahalanobis), de modo a identificar qual é o mais adequado para uma base de dados arqueológicos. Utilizou-se uma base de dados fornecida pelo Grupo de Estudos Arqueométricos do IPEN CNEN/SP, na qual foram analisadas 146 amostras de fragmentos cerâmicos de três sítios arqueológicos por análise por ativação com nêutrons instrumental, sendo determinadas as frações de massa de 24 elementos químicos: As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn. Para a determinação do melhor método, foram avaliados os dendrogramas conjuntamente com o valor dos coeficientes de correlação cofenética (CCC), obtidos para cada método. O método da ligação média mostrou-se mais coerente na formação dos agrupamentos, apresentando também os maiores valores do CCC. Por último, um script com funções do programa estatístico R foi desenvolvido para calcular o CCC, com o intuito de auxiliar os pesquisadores a encontrar o método de agrupamento mais apropriado para sua base de dados.
The objective of this work was to study the hierarchical methods of cluster analysis (single linkage, complete linkage, average linkage, centroid and Ward with base in the Euclidean distance, Squared Euclidean distance, Manhattan and Mahalanobis) to identify which is the most appropriate in archaeological data set. It was used a data set provided by the Archaeometry Studies Group from IPEN CNEN/SP in which 146 samples of ceramic fragments from three archaeological sites analyzed by instrumental neutron activation analysis, being determined the mass fractions of 24 chemical elements: As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn. For the determination of the best method, it was evaluated the dendrograms together with value of the cophenetic correlation coefficient (CCC) obtained for each method. The average linkage method was more coherent in formation of the clusters, and with higher CCC values. Finally, a script with functions of the R statistical software was developed to calculate the CCC with aim to be a tool for researchers find the most appropriate method of cluster analysis for their data set.

La present Tesi doctoral pretén aportar noves dades sobre les produccions de ceràmica valenciana d’època medieval i post-medieval. A partir del desenvolupament de l’especialització del treball que suposen les produccions preindustrials, s’ha procurat aprofundir en l’estudi de la societat valenciana. Per a tal tasca, s’han analitzat mitjançant les tècniques arqueomètriques les produccions ceràmiques majòliques com a indicadors del desenvolupament econòmic a partir de termes de comerç, intercanvi i difusió de les produccions. El cas de les majòliques és clau en el sentit que és molt més que un element de cultura material funcional, al portar implícits certs aspectes culturals relacionats amb la identitat i, també, l’estatus. A la vegada s’han valorat les innovacions tècniques a partir de la sistematització tipològica procurant veure els canvis experimentats al llarg dels segles en les formes més comunes, determinant les desaparicions de certes formes, el sorgiment de noves i valorant la continuïtat d’algunes d’elles. Amb la confluència de l’arqueologia i l’arqueometria s’ha volgut determinar les principals produccions a partir de l’estudi dels centres productors i la comercialització dels seus productes resultants a partir de l’estudi dels centres de consum. En tot moment s’ha tingut present que no només viatgen els productes. Al llarg de la història s’han produït intercanvis de coneixements entre les persones, els quals poden ser observats amb la mobilitat d’artesans tant a nivell peninsular com extra-peninsular. Tradicionalment s’ha parlat de València com a centre productor, però per poder verificar-ho es precisa la identificació de les produccions ceràmiques, valorant la seva evolució formal i tècnica i les distribucions d’aquests materials. Si ens guiem per les fonts escrites de l’època, es considera que entre els segles XV i XVIII, existien a l’àrea de València com a mínim 14 centres de producció, entre els quals es trobava la pròpia ciutat de València. Això no obstant, el coneixement arqueològic d’aquesta realitat és molt pobre amb evidències desiguals de pocs jaciments. Les excepcions són els centres de Paterna i Manises que semblen tenir activitats contínues des de temps medievals. Per establir les bases d’aquesta línia d’investigació plantegem l’aplicació de l’arqueometria sobre ceràmiques arqueològiques per obtenir informació que ens ha de servir com a indicador de la provinença i de la tècnica de producció que s’ha seguit per a la seva elaboració. Per obtenir tal informació, s’ha procedit a la caracterització química i mineralògica, amb una sèrie de tècniques analítiques que seran exposades més endavant. El fet d’analitzar aquests aspectes composicionals ens porta a la comprensió de la vessant natural de la ceràmica, les matèries que la formen, alhora que ens permet efectuar aproximacions a les tècniques productives i les voluntats dels ceramistes per garantir que les peces satisfessin unes funcionalitats determinades.
This investigation aims at rethinking the medieval and post-medieval Valencian majolica through archaeology and archaeometry. The main objectives are to develop a new systematised typology and to define the products of the Valencian workshops and their diffusion. The first part of the project consists of the archaeometric characterisation of the production centres. For this reason, samples from Potries, València and Manises, recovered from well-known archaeological contexts with clear stratigraphic sequences, have been sampled, and some of them have been analysed. According to the archives, between the 15th and the 18th centuries, at least fourteen pottery production centres were located in the area of València, including València itself. However, the archaeological record is scarce and fragmented except for Paterna and Manises, where potters produced majolica from a period that lasted from the 13th to the 18th centuries. This research aims, ultimately, to contribute to improving knowledge about Valencian workshops, including those previously studied, such as Manises. The second part of the project is based on some Catalan consumption centres to determine the distribution of the Valencian products in this area, mainly Barcelona and Santa Creu de Rodes. All the individuals have been chemically characterised through x-ray fluorescence analysis (XRF) and mineralogically through x-ray diffraction analysis (XRD). The new data obtained in this study have been compared with the ARQUB database, which includes all the majolicas, or tin-glazed pottery, and other modern pottery from the Iberian Peninsula studied to present by the members of the team. The archaeometric results have been integrated with the archaeological information about the sites, decoration and morphometric characteristics of these ceramics, and the written sources. The results obtained demonstrate the existence of great complexity of the ceramic production at València and shows the necessity of archaeometric studies to identify the imitations. Finally, it is confirmed that Valencian products were involved in a significant expansion through the Mediterranean Sea.