Aspectos arqueométricos en restos óseos. Ensayo metodológico

The purpose of this work is the presentation of the main results of a methodological palaeodiet test through trace elements analysis in skeletal remains. The method used to analyze the bone samples is Inductively Coupled Plasma Opltical Emission Spectrometry (ICP OES). This research takes into account diagenic factors applying a method of control for a better reading of the results. The data obtained show trace elements values indicators of a vegetable diet and trace elements values indicators of a meat diet related with contaminated factors which take part post- mortem

Western mediterranean archaeology: chemical element levels in archaeological materials as a methodological tool

Una línea de desarrollo de las investigaciones arqueométricas, objeto de nuestro estudio, que presenta un amplia gama de potenciales aplicaciones metodológicas, al día de hoy conocidas solo en parte, es el análisis de los elementos químicos metálicos y no metálicos, ya sean los elementos mayoritarios, los elementos trazas y, más recientemente, los conocidos como “tierras raras” (por su nombre en inglés, Rare Earth Elements - REEs), que se han revelado útiles en nuestro estudio para la solución de algunos problemas arqueológicos. La posibilidad de poder actuar de forma sistemática, ha ayudado, por un lado, a conocer y desarrollar el potencial de estos elementos y, por otro, ha servido de soporte para ofrecer la solución de problemas metodológicos en un conjunto de materiales arqueológicos muy heterogéneos, que contemplan en primer lugar el análisis de restos óseos procedentes tanto de cremaciones, como de inhumaciones, y con menor alcance los análisis de sedimentos arqueológicos y también tejidos humanos momificados y material asociado al contexto de sepultura como la madera de los ataúdes y los tejidos de las vestimentas. El objetivo general de este proyecto es investigar las potencialidades de los elementos metálicos y no metálicos a través del análisis de diferentes materiales arqueológicos, para concretar una serie de propuestas metodológicas experimentales aplicadas de manera específica teniendo en cuenta el material y el contexto arqueológico tratados. Al mismo tiempo, se propone una metodología analítica reproducible y precisa en los resultados que permitirá obtener un análisis estadístico significativo y fiable. Los objetivos específicos consisten en: Definir una estrategia para una correcta selección de muestras de huesos quemados e inhumados a través de la identificación de su perfil elemental por medio del análisis químico de tierras raras (REEs) elementos traza y elementos mayoritarios, desarrollando un método basado en el empleo de herramientas estadísticas para el control de los factores diagéneticos y un modelo de clasificación multivariante para la identificación de muestras de hueso con un perfil elemental biológico mejor conservado y así abordar estudios biológicos o de paleodieta, excluyendo las conclusiones erróneas inducidas por los factores diagéneticos. A raíz de la metodología desarrollada para el estudio de los huesos se han desarrollado ensayos metodológicos en diferentes materiales. Con el análisis de restos arqueológico-forenses se intenta concretar una estrategia para una correcta interpretación de los resultados de metales pesados (arsénico -As-, mercurio- Hg- y plomo-Pb-) en huesos y tejido humano momificado, desarrollando un método basado en la selección de muestras para el control de los factores diagenéticos y la identificación de muestras con valores de As, Hg y Pb antemortem mejor conservados, para así poder abordar estudios de arqueología-forense de casos de envenenamiento excluyendo conclusiones erróneas inducidas por procesos postmortem. Las técnicas empleadas están basadas en la espectrometría atómica. Principalmente se han muestreado huesos inhumados, quemados y suelos, y también tejidos humanos momificados, maderas y tejidos textiles, aunque estos últimos tres materiales están presentes en un número inferior de muestras. Se han utilizado técnicas de muestreo diferentes dependiendo del tipo de material y su estado de conservación.This dissertation has developed new methodological skills applied to archaeometry using Rare Earth Elements (REEs), major and trace elements analysis. The study of these chemical elements has revealed their potentiality, useful to solve different archaeological problems. A large number of samples have been collected (522) and around 1600 samples have been analyzed taking into account the dilutions and the different instruments employed. The capability to act consistently has helped to understand the behaviour of the elements and has provide the support to present new methodological proposals for a set of very heterogeneous and diachronic archaeological materials such as skeletal remains from inhumations, cremations and also sediments, mummified human tissues, wood and textiles

Chemical characterisation of cherts from the valley of Serpis river (Alcoy, Alicante) for archaeological purpose

Mobility range and territorial control are central questions for Archaeology in the study of human groups’ life during Prehistoric Ages. A key point to get to grips with this set of problems is to understand the dynamics of supply of natural resources such as food and raw materials. Thus, the identification of the outcrops of chert and their characterisation is essential, due to the use of this particular rock as raw material for the production of several different tools. Since the nakedeye description of stone characters (colour, translucency, presence of carbonatation or patina, etc.) often lacks to identify different outcrops and to determine the provenance of a sample, in the last decades, scientists have tried to develop methods to improve the characterisation of this rock from the chemical, mineralogical and petrographic point of view [1,2]. This contribution shows the study of some chert varieties which were widely used since the Paleolithic by the inhabitants of the valley of Serpis river [3], in the southern part of the Valencian Community. Forty-three samples of Serrat, Mariola and Serreta chert were collected from different kinds of outcrops: from the wall rock, and from fluvial and colluvial deposits. The cortex or crust and the nucleus of each sample were mechanically separated and individually analysed to control the variability caused by the amount of cortex and consequently to develop a methodological approach that permits to identify different chert sources in a restricted area. For this purpose, Xray fluorescence and Inductively coupled plasma mass spectrometry analyses have been carried out to determine major elements, trace elements and rare earth elements [4] of cherts affected by different depositional and post-depositional conditions. [1] Luedtke, An Archaeologist's Guide to Chert and Flint (1992) 172. [2] Skarpelis et al., J. Archaeolog. Sci.: Rep. 12 (2017) 819. [3] Molina Hernández, El sílex del Prebético y cuencas neógenas en Alicante y sur de Valencia :su caracterización y estudio aplicado al Paleolítico Medio, tesis doctoral (2015) 902. [4] Murray, Sediment. Geol. 90 (1994) 213

Archaeometric study of mortars from the Pisa's Cathedral Square (Italy)

The present work is focused on the study of forty-two mortars used in the construction of both Roman buildings, old Pisa’s Cathedral and Modern structures in the Miracles Square (Italy). This area, included since 1987 in the World Heritage List of the UNESCO, is famous for the presence of an important historical complex built in the Middle Ages (the Cathedral, the Baptistery, the Leaning Tower and the Monumental Cemetery). The archaeologists discovered some structures related to more ancient periods: the Roman domus (1st–5th centuries) and the older cathedral with its foundations and crypt (10th century). Based on OM, XRF, XRPD, TG-DSC and SEM-EDS analyses, the main characteristics of binder and aggregate of the mortars have been determined, and some raw materials used for the production of the analysed binding materials have been identified

Lanthanides Revealing Anthropogenic Impact within a Stratigraphic Sequence

Difficulties to differentiate between anthropogenic and natural processes in the formation of archaeological deposits are crucial for a correct interpretation not only of the actions involved in the development of archaeological sites, but also of their occupation- abandonment dynamics and the understanding of their spatial behaviors and relationship with the environment. We have carried out lanthanides (rare earth elements ¿REE¿) analysis to distinguish anthropogenic from natural stratigraphic units in sediments using the advantage of the high sensibility, precision, and accuracy of ICP-MS measurements. In the Neolithic site of Mas d¿Is (Alacant, Spain), we have applied REE analysis in a huge stratigraphic sequence called Pit 6, which was known to contain a large anthropogenic component. Randomly collected soil samples were sequentially taken in order to identify anthropogenic soil formations and to prove the proposed method blind testing has been used. In the specific case of Mas d¿Is excavation a recurring question is whether paleosols are at the origin of the human occupation of the sites or it was the occupation of this areas which triggered the paleosols development. Our purpose was to distinguish the degree of human contribution to paleosols formation between samples sequentially taken at few centimeters of distances in a giant stratigraphic sequence (Pit 6) employing REE analysis

Prediction of alkaline earth elements in bone remains by near infrared spectroscopy

An innovative methodological approach has been developed for the prediction of the mineral element composition of bone remains. It is based on the use of Fourier Transform Near Infrared (FT-NIR) diffuse reflectance measurements. The method permits a fast, cheap and green analytical way, to understand postmortem degradation of bones caused by the environment conditions on different skeletal parts and to select the best preserved bone samples. Samples, from the Late Roman Necropolis of Virgen de la Misericordia street and En Gil street located in Valencia (Spain), were employed to test the proposed approach being determined calcium, magnesium and strontium in bone remains and sediments. Coefficients of determination obtained between predicted values and reference ones for Ca, Mg and Sr were 90.4, 97.3 and 97.4, with residual predictive deviation of 3.2, 5.3 and 2.3, respectively, and relative root mean square error of prediction between 10% and 37%. Results obtained evidenced that NIR spectra combined with statistical analysis can help to predict bone mineral profiles suitable to evaluate bone diagenesis

Niveles de plomo en los individuos de la necrópolis tardorromana de la c/ Virgen de la Misericordia (Valencia)

El objetivo general de este estudio ha sido determinar los contenidos de plomo (Pb) en restos de huesos y suelos de la necrópolis de la c/ Virgen de la Misericordia (Valencia) para reconstruir el proceso de transición del elemento (desde el sedimento hacia los huesos y viceversa) debido a la acción de los procesos diagenéticos

Análisis químicos no destructivos sobre cinco mangos de marfil de Época Ibérica

Presentamos los análisis químicos realizados sobre un conjunto de cinco mangos de marfil época ibérica (s. VI – s. I a. C.). Son objetos con características técnicas, formales y decorativas muy similares entre sí, lo que que permite plantear una relación entre ellos en su proceso de producción. Sin embargo, fueron recuperados en cuatro yacimientos diferentes del área ibérica: los poblados de Turó de Montgròs (El Brull, Barcelona) y La Serreta (Alcoi, Alicante) y las necrópolis de El Cigarralejo (Mula, Murcia) y Coimbra del Barranco Ancho (Jumilla, Murcia), en esta última, se recuperaron dos de ellos. Todas las piezas, por sus contextos arqueológicos se datan entre el s. IV y principios del s. II a. C. Los análisis se llevaron a cabo con el objetivo de identificar la naturaleza y procedencia de las incrustaciones de carácter decorativo y la sustancia adherente todavía presentes en estos mangos. Si bien, en algunos de ellos, debido a su deteriorado estado de conservación, únicamente quedaban las improntas de las incrustaciones y no había restos aparentes de la sustancia de tono gris-negro que, presumiblemente, serviría para adherir las incrustaciones. Las piezas mejor conservadas son las recuperadas en lugares de hábitat. Los estudios se han realizado mediante técnicas no destructivas que no comprometiesen la integridad de las piezas. Así, se llevaron a cabo análisis por Fluorescencia de Rayos X (XRF), y por Espectrofotometría de Infrarrojo Cercano por Transformada de Fourier (FT-NIR). Todo ello se complementó mediante la revisión de los mangos con un microscopio electrónico de barrido equipado con un Sistema de Rayos X de Energía Dispersiva (SEM-EDAX-Sapphire), un microscopio óptico SMZ (NIKON) y un microscopio digital Dino-lite mod. AM7115MZT EDGE de 10x a 200x con una luz incidente por medio de un iluminador de fibra óptica y dotado de un software con funciones de medición integrales, para obtener imágenes de alta precisión. El análisis de XRF ha permitido identificar como estaño la sustancia empleada para adherir las incrustaciones decorativas en la pieza, empleando una técnica de tipo soldadura blanda. El FTNIR, por su parte, ha revelado que dichas incrustaciones fueron realizadas sobre resinas fósiles, muy probablemente ámbar. Estos resultados resultan totalmente novedosos dentro del mundo artesanal de época ibérica y, por tanto, de gran interés, evidenciando el valor de estas piezas en las que materias primas de presencia escasa en el mundo ibérico como son el marfil y el ámbar aparecen combinadas; así como el uso del estaño a modo de soldadura blanda nos revela procesos de manufactura no atestiguados hasta el momento en las industrias sobre materias duras de origen animal de la Edad del Hierro en la Península Ibérica. Cabe destacar que la realización de análisis químicos sobre piezas arqueológicas aporta datos específicos, prácticamente imposibles de obtener en un estudio macro o microscópico de los artefactos. Por ello, desde el proyecto proyecto “Madera, hueso, marfil, asta, concha ¿Artesanías marginales o marginadas?” (HAR2013-45770-P y ACOMP/2015/256) (financiado por el Ministerio de Economía y Competitividad y la Generalitat Valenciana) dirigido por la Dra. Consuelo Mata, se ha apostado por desarrollar estudios interdisciplinares, que impliquen el contacto y la comunicación entre distintos especialistas con la finalidad de conseguir resultados más sólidos y transversales

Rare Earth Elements to identify archaeological strata in the Cocina Cave

Rare earth elements (REE) have been employed in a variety of different scenarios in order to identify the natural or anthropogenic nature of archaeological soils [1,2] . In this study, REE signatures were employed to better understand the layers formation in a cavity called Cocina cave, a large cavity of 300 m2 located at Barranco de la Ventana, one of the ravines flowing southwards from La Canal valley, a little plateau located in the municipality of Dos Aguas (Valencia, Spain). Cocina cave is characterized of very homogenous sediment deposition where it is difficult to understand layers formation processes just employing the traditional archaeological methods and the standardized soil analyses. The archaeological sequence encompasses last hunter-gatherer Holocene occupations in the regional sequence (Mesolithic) followed by several levels attributed to the Neolithic, Bronze Age and historic occupations until the XX century, these last regarding the use of the cavity as a pen. In order to understand the development history of the strata and the anthropogenic or natural formation of soils a total of fifty samples were taken across six different sections (A, B, C, D, E, F, G) and from each section the sampling was carried out at different depths through 1-2m deep sections. All samples were recovered from current pits excavated at the cavity corresponding with some profiles that encompass different strata including natural deposits and hunter and penning activities together with other possible uses not well defined from archaeological data. Several radiocarbon dates confirm the anthropogenic use of the cavity from the IX millennium cal BP to the contemporary times. Major, minor and trace elements including REE were determined employing XRF and ICP- MS. Results were then statistically processed and cross-referenced with archaeological data to aid interpretation. The results show that REE provide interesting details regarding the strata development history, and therefore help archaeologists to better understand the occupation, use and abandonment phases of the cave. [1] Pastor et al., TrAC 78 (2016) 48. [2] Gallello et al., JAS 40 (2013) 799

Archaeometric study of mortars from the Pisa’s Cathedral Square (Italy)

The present work is focused on the study of forty-two mortars used in the construction of both Roman buildings, old Pisa’s Cathedral and Modern structures in the Miracles Square (Italy). This area, included since 1987 in the World Heritage List of the UNESCO, is famous for the presence of an important historical complex built in the Middle Ages (the Cathedral, the Baptistery, the Leaning Tower and the Monumental Cemetery). The archaeologists discovered some structures related to more ancient periods: the Roman domus (1st – 5th centuries) and the older cathedral with its foundations and crypt (10th century). Based on OM, XRF, XRPD, TG-DSC and SEM-EDS analyses, the main characteristics of binder and aggregate of the mortars have been determined, and some raw materials used for the production of the analysed binding materials have been identified