Burned bones forensic investigations employing near infrared spectroscopy

The use of near infrared (NIR) spectroscopy was evaluated, by using chemometric tools, for the study of the environmental impact on burned bones. Spectra of internal and external parts of burned bones, together with sediment samples, were treated by Principal Component Analysis and cluster classification as exploratory techniques to select burned bone samples, less affected by environmental processes, to properly carry out forensic studies. Partial Least Square Discriminant Analysis was used to build a model to classify bone samples based on their burning conditions, providing an efficient and accurate method to discern calcined and carbonized bone. Additionally, Partial Least Square regres…

Chemical Element Levels as a Methodological Tool in Forensic Science

The aim of the present study was to define a methodological strategy for understanding how post- mortem degradation in bones caused by the environment affects different skeletal parts and for selecting better preserved bone samples, employing rare earth elements (REEs) analysis and multivariate statistics. To test our methodological proposal the samples selected belong to adult and young individuals and were obtained from the Late Roman Necropolis of c/Virgen de la Misericordia located in Valencia city centre (Comunidad Valenciana, Spain). Therefore, a method for the determination of major elements, trace elements and REEs in bone remains has been developed employing Inductively-Coupled Pla…

Indirect chronology method employing rare earth elements to identify Sagunto Castle mortar construction periods

A novel indirect chronology method has been developed to identify Sagunto Castle construction periods. The method is based on the use of inductively coupled plasma mass spectrometry (ICP-MS) to determine rare earth elements (REE) and other trace elements in mortars. Additionally, a no destructive geochemical analysis based on X-ray fluorescence (XRF) was employed for major elements determination. Collected chemical data were processed through Principal Component Analysis (PCA) to highlight any differences among the mortars belonging to different buildings and construction periods. The results show that PCA analysis permits to discriminate construction periods according to mortar sample REE …

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 sop…

Regional provenance of dolerite prehistoric objects through mineral analysis

Abstract A methodology based on the mineral analysis determination has been developed to identify the origin of dolerite stone outcrops collected to fabricate lithic objects during the Prehistoric period. The method is based on the use of inductively coupled plasma mass spectrometry (ICP-MS) to analyse rare earth elements (REE) and trace elements. Additionally a no destructive geochemical analysis based on X-ray fluorescence (XRF) was employed for major elements analysis. The aforementioned methodologies were applied to samples from different archaeological fields or natural outcrops located in the Mediterranean area of Spain, between Valencia and Alicante. Principal component analysis (PCA…

Developing REE parameters for soil and sediment profile analysis to identify Neolithic anthropogenic signatures at Serpis Valley (Spain)

In this study, patterns of rare earth elements (REE) have been developed and applied for the first time to sediments and soils to identify anthropogenic or natural layers in profiles sampled at several Neolithic settlements in the Serpis Valley area (Alicante, Spain). Most of these sites are characterized by dark brown paleosols that are easily distinguishable from the light brown paleosols of the valley. To demonstrate whether these strata are anthropogenic or natural requires a better geochemical understanding of sediment. Soil samples were taken across six different sites; four sites are associated with archaeological findings (sites BF, LP, PB and AC8); another one is from a natural sec…

El método del caso como herramienta de aprendizaje activo en arqueología

[EN] The case study, like other methodologies that enhance the active participation of the students, greatly favours the teaching-learning process. Here we present the design, application and results of the cases implemented in two Archaeology subjects (History Degree, University of Valencia). Within the framework of a Teaching Innovation Project (METARQ), we have implemented, in six different groups, two cases related to two subjects: Archaeological Methodology (3rd year-2nd semester, three groups) and Mediterranean Archaeology (4th year-1st semester, three groups). Both the learning results and the general opinion of the students were very positive. In addition, the application of this po…

Variación química intrasquelética relacionada a la diagénesis en los restos óseos de c/En Gil (Valencia)

El objetivo de esto estudio ha sido definir una estrategia para una correcta selección de muestras de huesos inhumados (femures y costillas) menos afectados por los procesos diagéneticos, determinado los contenidos de elementos mayoritarios, trazas y REEs. Intentando en este modo  de reconstruir el proceso de transición de los elementos  desde el hueso al depósito tafonómico y viceversa. Una atenta selección de las muestras  es determinante para que los análisis químicos  puedan contribuir correctamente a una reconstrucción de la alimentación, las dinámicas de desplazamiento y las enfermedades de las poblaciones antiguas. Las  muestras analizadas pertenecen a individuos hallados en las necr…

Non-destructive analytical methods to study the conservation state of Apadana Hall of Persepolis.

Atmospheric and biological agents are the main enemies of the building material conservation. In this work an innovative methodological approach, based on Near Infrared Spectroscopy (NIR) and X-Ray Fluorescence Spectroscopy (XRF), has been employed to evaluate the conservation state of Persepolis limestone samples collected both, under a protective shelter and outside the shelter, at Apadana Audience Hall area in Persepolis. The use of NIR spectra permitted to discriminate, by using Principal Component Analysis (PCA), the differences between samples collected inside and outside the protective shelter and we have been able to identify a major degradation state of the out shelter stone sample…

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.

Respuesta docente frente a la pandemia de la COVID-19: el uso de Blackboard y Flipped Teaching en la asignatura de Metodología Arqueológica

[ES] El sistema educativo universitario se basa en gran medida en clases presenciales. Un evento inesperado como la pandemia de la COVID-19, que estalló durante los primeros meses del 2020, llevó a las autoridades a declarar el estado de alerta y a tomar, entre otras medidas, la interrupción de la actividad docente presencial. El profesorado universitario tuvo que adaptar la actividad docente a un sistema, para muchos, novedoso: la docencia en línea. Este trabajo tiene como objetivo mostrar los instrumentos y las estrategias empleadas para dar una rápida respuesta a una situación de emergencia. Nuestro caso se centra en la enseñanza de una asignatura de tercer curso del Grado de Historia en…

The capability of Rare Earth Elements geochemistry to interpret complex archaeological stratigraphy

Abstract In this study rare earth elements (REE) signatures (REE ratios, cerium and europium anomalies) are applied to a complex soil stratigraphic sequence from the site of Konso, Ethiopia, with the aim of determining whether REE can distinguish the strata observed in the field. Forty soil samples were taken from a depositional sequence that includes overlapping human induced and ‘natural’ erosional and depositional processes. The samples were analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to determine trace elements and REE, with concentrations of major elements determined using X-ray fluorescence (XRF). Cluster Analyses (CA) were used to observe differences between str…

El prestigio de los objetos: mangos de marfil en el mundo ibérico

El estudio se centra en una serie de mangos de marfil de características morfotécnicas similares, recuperados en espacios de hábitat y funerarios ibéricos y datados entre el s. IV y el s. II a. C. Se trata de objetos de prestigio al alcance de una élite aristocrática, que han sido elaborados con materias primas exóticas (marfil) y técnicas decorativas inusuales que indican una especialización. A través de análisis de composición por infrarrojo cercano por Transformada de Fourier (FT-NIR) y de fluorescencia de rayos X (pXRF) se ha podido documentar la presencia de incrustaciones de ámbar adheridas a la superficie de los mangos mediante el uso del estaño como soldadura blanda y el empleo de a…

Analysis of Sagunto Ibero-Roman votive bronze statuettes by portable X-ray fluorescence

Abstract The main objective of this work was the study of chemical composition of an important collection of Ibero-Roman votive bronze statuettes exposed in the Archaeological Museum of Sagunto (Spain). Precision and accuracy of the measurements were obtained developing a proper analytical method, also avoiding any possible damage to the studied objects using a portable energy dispersive X- ray fluorescence system. Principal Components Analysis (PCA) to discriminate between groups based on ratios Fe/Cu, Pb/Cu, Sn/Cu, Ag/Cu, Ni/Cu and Impurities/Cu were employed to observe differences between the used smelting, manufacturing processes and raw materials. The characterisation of bronze statuet…

Anthropogenic units fingerprinted by REE in archaeological stratigraphy: Mas d'Is (Spain) case

Abstract On occasions, archaeologists have to deal with serious difficulties to differentiate between processes that ultimately are responsible for the formation of stratigraphic units. Sometimes we face problems related with depositional units in multilayered deposits and other times, we ask for the character of some dark surface soils, very similar to natural paleosols and usually associated with archaeological findings. In both cases, the problems we must address concern the relative impact of human activities. The imbalance between anthropic and natural processes in the formation of archaeological deposits is crucial for a correct interpretation of the processes involved in the formatio…

Una pequeña lámina de plomo con inscripción ibérica de paleografía arcaica del Pico de los Ajos (Yátova, València)

espanolEn este trabajo editamos una pequena lamina de plomo hallada en el Pico de los Ajos (Yatova) en la campana de 2018. La lamina aparecio plegada y contiene una inscripcion iberica de una sola linea en cada cara que muy probablemente configure un solo texto completo. Sus caracteristicas formales son poco comunes, siendo el paralelo mas cercano el de las laminas votivas de El Amarejo. La presencia del elemento kutuŕ, frecuente en las inscripciones votivas rupestres, tambien apuntaria a una interpretacion religiosa. Desde el punto de vista paleografico, cabe senalar que se trata de un texto explicitamente dual, ya que conviven en el las dos variantes de te y ŕ. A pesar de que el contexto …

Characterization and sources of Paleolithic–Mesolithic ochre from Coves de Santa Maira (Valencian Region, Spain)

Chert Nucleus and Cortex Characterization for Archaeological Provenance Study Tested in the Prebaetic System Region (Valencian Community, Spain)

The characterization of chert artifacts and the identification of their raw material is a pivotal issue in archaeology for the comprehension of economic and territorial patterns related to prehisto...

Biological mineral content in Iberian skeletal cremains for control of diagenetic factors employing multivariate statistics

Abstract The aim of this study was to define a strategy for a correct selection of bone samples by employing inductively coupled plasma optical emission spectroscopy (ICP-OES) for reconstructing the biological mineral content in bones through the determination of major elements, trace elements and Rare Earth Elements (REE, lanthanides) in skeletal cremains of ancient Iberians (III–II B.C), discovered in the Necropolis of Corral de Saus (Moixent, Valencia) between 1972 and 1979. The biological mineral content was determined taking into account diagenetic factors. A control method for a better reading of results was applied. To explore large geochemical datasets and to reduce the number of va…

Analysis of stratigraphical sequences at Cocina Cave (Spain) using rare earth elements geochemistry

This study investigates the stratigraphical sequence of Cocina Cave (Spain) employing and testing for the first time the capability of rare earth elements as markers of human activities in caves. Located in Dos Aguas (Valencian Community, Spain), Cocina Cave is characterized by the presence of several Holocene archaeological deposits from the final Mesolithic to the present day and is a pivotal site for understanding the socio‐ecological dynamics of the last hunter‐gatherer inhabitants of the Iberian Peninsula and the transition to pastoral and agricultural economies in the Western Mediterranean. However, the identification of strata from particular time‐periods in the cave is often difficu…

Chemical and mineralogical analyses on stones from Sagunto Castle (Spain)

Abstract For the first time, an archaeometric study was carried out on the carbonate rock ashlars of the Sagunto Castle. The studied site is one of the most important and best preserved Spanish archaeological and architectural monuments, characterized by different construction phases from the Roman period to Modern Ages. Forty samples collected from thirteen different structures of Sagunto Castle and two quarries, located in the Sagunto's hill were used for comparative purposes. The samples were analyzed by X-ray diffraction, X-ray fluorescence and inductively coupled plasma mass spectrometry to determine their mineralogical and elemental composition. The obtained data show similar chemical…

An innovative multi-analytical approach based on spectroscopic and electrochemical techniques to study a complex Roman amphorae collection

Abstract An innovative multi-analytical approach for the classification of ancient pottery sherds was tested. Twenty Roman amphorae fragments belonging to different known typologies and twenty-seven unclassified ones from a complex Sagunto Archaeological Museum (Spain) collection were studied by multielement analysis (X-ray fluorescence spectroscopy and inductively coupled plasma mass spectrometry), Fourier-transform near infrared spectroscopy and voltammetry of immobilized microparticles employing a minimal amount of sample. Chemometric analysis based on principal component analysis allowed the identification of most of the unclassified samples, proving the importance and reliability of th…

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 post-mortem 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. Coef…

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 hu…

Poisoning histories in the Italian renaissance: The case of Pico Della Mirandola and Angelo Poliziano.

Giovanni Pico della Mirandola and Angelo Poliziano were two of the most important humanists of the Italian Renaissance. They died suddenly in 1494 and their deaths have been for centuries a subject of debate. The exhumation of their remains offered the opportunity to study the cause of their death through a multidisciplinary research project. Anthropological analyses, together with documentary evidences, radiocarbon dating and ancient DNA analysis supported the identification of the remains attributed to Pico. Macroscopic examination did not reveal paleopathological lesions or signs related to syphilis. Heavy metals analysis, carried out on bones and mummified tissues, showed that in Pico's…

A smartphone-based innovative approach to discriminate red pigments in roman frescoes mock-ups

The characterization of red pigments in frescoes wall paintings has been of great interest for researchers to better understand raw material procurement dynamics, pigment receipts, stylistic evolution and to assess their conservation state. In this study a non-destructive colorimetric approach implementing a smartphone-based method was developed in order to be able to distinguish between three pigments made from minium, haematite and cinnabar minerals, and also mixed pigments, preparing frescoes mock-ups following the roman receipt described by Vitruvius. Portable FT-IR, Raman spectroscopy, portable XRF and visible reflectance spectra analyses were carried out as reference methods for smart…

Gold-nanoparticles ingestion disrupts reproduction and development in the German cockroach.

The present work shows the effects of gold nanoparticles (AuNPs) orally administered on reproduction and development of the insect Blattella germanica. Newly emerged females were provided with food containing AuNPs (87.44μg/g) of a size between 15 and 30nm (mean 21.8nm), and were allowed to mate with males. Food ingestion, mortality, reproductive parameters (time to ootheca formation and eclosion, ootheca viability and fertility) as well as postembryonic developmental parameters of the first ootheca (nymphal survival and life span) were recorded throughout the experiment. Gold from AuNPs was accumulated by adults of B. germanica with a bioaccumulation factor of 0.1. Ingestion of AuNPs did n…

Aspectos arqueométricos en restos óseos. Ensayo metodológico

Social and technological changes in the ceramic production of the Northern Levant during the LBA/IA transition: New evidence about the Sea People issue through archaeometry

Abstract The transition from the Late Bronze Age (LBA) to the Iron Age (IA) in the Levant is marked by the collapse of the Egyptian and Hittite empires, which dominated the political scene of the 14th–13th century BCE. The role of the Sea People, groups of migrants who were defeated by the Egyptian king Ramses III around 1175 BCE, is the focal point concerning this period. After the collapse of the LBA empires, written sources disappeared, and the archaeologists’ primary tool to define cultural processes is to analyze the evolution of pottery. Because of this, studies about the distribution of Aegeanizing ceramic production, considered here to have derived from the Sea People culture, can p…

Ceramic productions and human interactions during the Early Bronze Age in northern Iberia

The Early Bronze Age ceramic collection found into the caves of La Llana and El Toral III in Asturias (Spain) presents common decoration such as that found in the centre of Cantabrian Spain from the same period, which resembles others found in the Ebro Valley and Atlantic Europe. Therefore, the main objective of this study it is to identify the raw material origin and understand the pottery production process during the Early Bronze Age in the Cantabrian region. A methodological approach based on the chemical and mineralogical analysis of vessels and experimentally fired clay samples collected all over the centre of this region was developed. Furthermore, the post-depositional processes aff…

Mineral soil composition interfacing archaeology and chemistry

Abstract In the last decade, different soil types have been analysed to evaluate the effect of human activities from an archaeological point of view. In particular, in the last few years, tremendous advances have been made in sample preparation and analytical methods used in archaeological soil analyses. However, there is still a need to set standardized protocols to achieve different archaeological goals. Therefore, in this study, the analytical methods available to study archaeological soils have been reviewed together with a critical discussion on the challenging archaeological questions, which could be answered by determining their mineral composition. Data on trace elements and rare ea…

Assessing the territorial influence of an Iberian worship site. The chemical characterisation of the terracotta from the Iron Age sanctuary of La Serreta

This paper presents the study of the prestigious terracotta votive figurines from the Iberian Iron Age sanctuary of La Serreta (Alicante province, Spain) composed of 174 items. Portable X-ray fluorescence (PXRF) was used to identify elemental markers that permit us to observe the differences between local and non-local terracotta figurines and furthermore to evaluate the geographical influence of the La Serreta sanctuary using Principal Component Analysis (PCA). The Partial Least Squares Discriminant Analysis (PLSDA) statistical method was also used to classify the figurines of uncertain geographical origin. The resulting groups were related to typological and stylistic groups of figurines …

Decoration composition of Iberian Iron Age ivory artifacts identified by no-destructive chemical analyses

Se analizan mediante análisis no destuctivos 5 mangos de marfil con decoración incrustada. Se detecta ámbar y estaño. In this work, five unique Iberian Iron Age handles have been studied. The use of portable X-ray fluorescence (pXRF) and Fourier transform near–infrared (FT-NIR) spectroscopy no-destructive techniques has allowed us to identify two raw materials (amber and tin) used to decorate the ivory handles.Due to the finesse of their inlaid decoration and the value and exoticismof thematerial employed for their manufacture, these ivory objects are really exceptional Iberian archaeology findings. Interestingly, it has been possible to determine that tin was used as an adherentmaterial to…