X-Ray Fluorescence (XRF) Spectroscopy

... Q. Zheng a , Corresponding Author Contact Information , E-mail The Corresponding Author , F. Dierre a , V. Corregidor b , R. Fernández-Ruiz c , J. Crocco a , H. Bensalah a , E ... [5] M. Roumié, F. Lmai, A. Awada, K. Zahraman, B. Nsouli, A. Zaiour, M. Hage-Ali, M. Ayoub and J ...

Over the last decade, the chemical analysis of archaeological bone has emerged a s a new method to address the dietary composition of past human populations. Paleodietary studies provide one means to obtain invaluable information regarding prehistoric intra-and inter-group behavioral differentiation. Unlike other prehistoric archaeological data, materials recovered from the mortuary context provide access to individual behavior. The total elemental and isotopic composition of bone record quantitative signatures of long-term individual dietary intake. These dietary signatures provide one means to make inferences about differential access to resources in prehistoric societies. Archaeological bone chemistry data can be used to establish prehistoric access to subsistence resources from different marine and terrestrial ecosystems by various individuals and territorial groups. The most reliable quantitative dietary information is derived from stable carbon and nitrogen isotope ratios in bone colla-gen. In contrast, in viuo elemental dietary signatures in bone mineral are obscured by postmortem chemical changes in the burial environment. Hence, accurate dietary inferences from inorganic bone apatite will depend on controls for these postmortem alterations. Schiffer's recent treatise, Formation Processes of the Archaeological Record (1987), provides a n explicit theoretical framework in which to address postmortem chemical changes in buried bone. Previous attempts to elucidate the nature of chemical interactions between buried bone and associated soils have been limited by their use of l) simple diffusion models , and 2) total elemental soil composition or acid soluble extracts rather than the soluble and exchangeable ions available to solution under field conditions. Models addressing the fossilization process in bone m u s t consider both ionic substitution and mineralization mechanisms of diagenesis. Current solubility profile techniques for the differentiation of biogenic and diagenetic chemical phases in fossil bone neglect ionic substitution. Ionic soil solution data from a n arid-land South Australian archaeologcal site are presented to demonstrate the importance of such information to the development and testing of these pre-dictive models.

Over the last decade, the chemical analysis of archaeological bone has emerged as a new method to address the dietary composition of past human populations. Paleodietary studies provide one means to obtain invaluable information regarding prehistoric intra- and inter-group behavioral differentiation.
Unlike other prehistoric archaeological data, materials recovered from the mortuary context provide access to individual behavior. The total elemental and isotopic composition of bone record quantitative signatures of long-term individual dietary intake. These dietary signatures provide one means to make inferences about differential access to resources in prehistoric societies. Archaeological bone chemistry data can be used to establish prehistoric access to subsistence resources from different marine and terrestrial ecosystems
by various individuals and territorial groups. The most reliable quantitative dietary information is derived from stable carbon and nitrogen isotope ratios in bone collagen. In contrast, in vivo elemental dietary signatures in bone mineral are obscured by postmortem chemical changes in the burial environment. Hence, accurate dietary inferences from inorganic bone apatite will depend on controls for these postmortem alterations.
Schiffer's recent treatise, Formation Processes of the Archaeological Record (1987), provides an explicit theoretical framework in which to address postmortem chemical changes in buried bone. Previous attempts to elucidate the nature of chemical interactions between
buried bone and associated soils have been limited by their use of l) simple diffusion models, and 2) total elemental soil composition or acid soluble extracts rather than the soluble and exchangeable ions available to solution under field conditions. Models addressing the fossilization process in bone must consider both ionic substitution and mineralization mechanisms of diagenesis. Current solubility profile techniques for the differentiation of biogenic and diagenetic chemical phases in fossil bone neglect ionic substitution. Ionic soil solution data from an arid-land South Australian archaeological site are presented to demonstrate the importance of such information to the development and testing of these predictive models.
The Roonka Flat Dune provides an excellent natural laboratory to address postmortem diagenesis in buried bone. The chemically homogenous sand dune was used as an Aboriginal burial ground during a major portion of the last 10,000 years. The ionically depleted soil solutions in this siliceous dune should limit both secondary mineralization and ionic substitution mechanisms of diagenesis. Thus, if bone mineral is ever expected to escape the ravages of postmortem chemical reactions this is one burial environment in which to test the null hypothesis. In order to address the various diagenetic mechanisms,
elemental ratios in the dune soil solutions were compared with those in rib bone from archaeological human skeletons and modern terrestrial mammal controls.
Even though significant diagenetic changes were not expected, the Roonka archaeological bone was enriched with Si, AI, Mn, Ba, Fe, S, Sr, K, and Ti and depleted in Mg relative to the modern controls. A variety of processes including physical contamination with quartz and secondary carbonates and ionic substitution from the soil solution are responsible
for these postmortem chemical alterations. The concentrations of the soluble alkaline earth metals Mg, Sr, and Ba increase relative to Ca with duration of burial, whereas the alkali metal K and the less soluble Ti, Si, Fe, AI, and Mn show no significant changes with time. The mobile Mg, Sr, and Ba occur in secondary minerals and substitute for Ca in the
hydroxyapatite lattice. In contrast, there is a rapid equilibration between the less soluble soil elements and the buried rib bone. It appears that the bone has been physically contaminated by sediments containing Ti, Si, Fe, Al, and Mn. Thus, diagenetic mechanisms involving secondary mineralization and ionic substitution from the soil solution are not likely
for these elements. These postmortem chemical changes will provide major obstacles to paleodietary inferences from the elemental composition of archaeological bone mineral. In the absence of
extensive archaeologically associated faunal controls with known diets, dietary inferences from elements in the inorganic apatite component of interred human bone will remain problematic.
Thesis on file at:
1) Australian Institute of Aboriginal Studies
2) Department of Prehistory, RSPacS, Australian National University
3) Department of Anthropology, University of Sydney
4) Division of Archaeology, South Australian Museum
5) Centre for Prehistory, University of Western Australia

Thermogravimetric and multi-element analyses of archaeological human rib and modern mammal controls from the lower Murray River region of South Australia indicate that magnesium, strontium, and barium concentrations in the archaeological bone have been altered significantly by post-mortem chemical reactions in the burial environment. Ionic exchanges between soil solution and buried bone resulted in lower bone magnesium concentrations and higher bone strontium and barium concentrations. Much of the remaining magnesium is associated with diagenetic calcite. Although the archaeological bone exhibits increased hydroxyapatite crystal size, the strontium and barium increases are not correlated with crystal growth. The complex interactions of these post-depositional chemical processes will complicate attempts to reconstruct in vivo elemental values from archaeological bone

Accurate paleoecological inferences from the elemental composition of human and faunal bone recovered from archaeological and paleontological sites will depend on controls for postmortem diagenesis. In vivo chemical signatures in bone can be obscured by postmortem changes in the soil environment. Models addressing the fossilization process in bone must consider both ionic substitution and mineralization mechanisms of diagenesis. Current solubility profile techniques for the differentiation of biogenic and diagenetic chemical phases in fossil bone neglect ionic substitution. Ionic soil solution data from an arid-land South Australian archaeological site are presented to demonstrate the importance of such information to the development and testing of these predictive models. Elemental ratios in the soil solution are compared with those in rib bone from archaeological human skeletons and modern terrestrial mammal controls. The archaeological bone is enriched with Si, AI, Mn, Ba, Fe, S, Sr, K and Ti and depleted in Mg relative to the modern controls. A variety of processes including contamination with quartz and secondary carbonates and ionic substitution from the soil solution are responsible for these postmortem chemical alterations.

The soluble and exchangeable ions for a soil profile from the Roonka archaeological site. Lower Murray Basin. South Australia. arc compared with the total elemental content of the soils. Since the chemical composition of postmortem ionic substitution phases and secondary minerals in archaeological bone will depend on the availability of
ions to the soil solution under field conditions, it is suggested that models addressing diagenesis in bone employ soluble and exchangeable ions rather than total elemental soil data.

Researchers in Gyeongju National Museum of Korea and Okayama Orient Museum in Japan conducted a joint research on some important ancient glass vessels and beads housed in Gyeongju National Museum. Abe Yoshinari in Tokyo University of Science and Madoka Murakushi in the University of Tsukuba were in charge of the analysis of chemical compositions on the glass vessels and glass beads respectively. Also, with the help of Conservation Science Division in National Museum of Korea, CT scans on the glass vessels were carried out. Finds are that a cobalt blue glass vessel and a glass bowl with cut-design excavated in the northern tomb of Hwangnamdaechong and a cobalt blue glass bowl unearthed in the tomb No. 4 of Angye-ri village are categorized as natron glass with low K2O and MgO. It is also found that a blue-colored glass vessel excavated in the southern tomb of Hwangnamdaechong is classified into the plant-ash glass group in Central Asia with high K2O.

Současné dvacetikorunové mince jsou vyrobeny z oceli plátované slitinou mědi a zinku v poměru 75:25. Mince jsou navíc na povrchu galvanicky pokovené slitinou podobného složení. Dvacetikoruny do roku 2012 jsou galvanicky pokovené slitinou mědi a zinku v poměru 72:28 (tolerance ± 1 %), mince ražené od roku 2012 včetně mají složení galvanické vrstvy 70:30 (tolerance ± 10 %). V rámci dobře zachovaných dvacetikorun (ze soukromé sbírky) lze konstatovat v podstatě dokonalé rozdělení naměřených dat do izolovaných skupin ve smyslu (i) před rokem 2012, (ii) od roku 2012 včetně a dokonce (iii) pamětní ražby z let 2018 a 2019. S využitím RFA je tedy možné, především u dobře zachovaných exemplářů, rozlišit nedestruktivně i poměrně nepatrné změny v povrchovém složení současných dvacetikorunových mincí.

This article demonstrates that distinct and coherent silver sources can be discriminated from surface composi-tional analyses. In the first large-scale study of Archaic (pre-479 BC) Athenian silver coins in museum collections around the world, we analysed 788 coins by Energy Dispersive X-ray Fluorescence (XRF) spectrometry with a mathematical correction to provide a reliable composition for key diagnostic elements. Principal Component Analysis reveals compositional patterns including at least one copper-lead-gold (Cu, Pb, Au) triplet with strong clustering of data. The pattern for bismuth (Bi) was similar to, but not as clear as Pb. Considering elemental compositions in combination with a die study and isotopic analyses in the literature, we reveal when Lavrion was the metal source from which Wappenmünzen and Owl coinage types were struck, providing important new understanding about Athenian history in the pivotal period of transition from tyranny to democracy in the late sixth century BC. Beyond this specific example, we contend that XRF spectrometry could have wider application in studies of ancient silver, not least for a simplified triage protocol to help determine which silver artefacts should be subjected to slower, more costly and invasive trace elemental and isotopic analyses.

A total of 212 pieces of glass fragments from Dariali Fort were scientifically analysed and classified into 12 compositional types by means of non-destructive X-ray fluorescence analysis. Twenty-eight pieces of plant ash glass and a piece of lead silicate glass were identified as imports, manufactured in Islamic territories, although some fragments were possibly recycled. Sixty-six pieces, including ten fragments of glass bangles, showed a characteristic composition, with a higher content of alumina, which suggests that they might be related to Byzantine Anatolian glass. The remaining 117 pieces of vessel glass are possibly local products made in Georgia or the surrounding area. Our scientific investigation of this glass has, therefore, demonstrated the import of glass products from both the Islamic world and Byzantine Anatolia into Georgia and raised the interesting possibility of large-scale glass production, using various colourants, in Georgia or the wider Transcaucasus region; although further verification focusing on production technique is needed. Especially, as pointed out above, quantification of light elements (B and Li) of these glasses will be necessary to evaluate the possibility that their raw material(s) were derived from borate deposits in Western Anatolia.

Özet
Manyas Gölü'nün (Bandırma, Balıkesir) güneydoğu kıyısında bulunan Daskyleion'un, yerleşim alanına ek olarak doğu ve güneyinde iki de nekropol alanı bulunmaktadır. Bu nekropol alanları, Daskyleion'un farklı dönemlerine ait çeşitli tip ve büyüklüklerde mezarları barındırmaktadır. Bu mezarlar arasında, Kaya Mezarı II olarak tanımlanan mezar, anakayaya oyulmuş uzun bir dromos ve mezar odasından oluşmaktadır. Mezarda 2014 yılında yapılan kazı çalışmalarında, anakayaya işlenmiş iki kline ile çeşitli tür ve biçimlerde ölü hediyeleri açığa çıkartılmıştır. Çalışmaya konu olan buluntu, bu klinelerden biri üzerine defnedilmiş olan bireye mezar hedi-yesi olarak bırakılmış çelikten yapılmış bir hançerdir. Kınıyla birlikte ve in situ olarak günü-müze kadar korunagelmiş olması, bu hançere Anadolu ve bölge arkeolojisi açısından ender bir buluntu niteliği kazandırmaktadır. Ankara Hacı Bayram Veli Üniversitesi, Tarihi Malzeme Koruma ve Araştırma Laboratuvarı (MAKLAB) bünyesinde arkeometrik yönden incelenen hançer üzerinde XRF, X-ışını radyografi, metalografi, SEM-EDX ve LIPS analizleri yapılmış-tır. Analizlerden elde edilen veriler ışığında, hançerin kimyasal kompozisyonu, üretim süreci ve olası hammadde kaynağı hakkında bilgilere ulaşılmıştır.

Abstract
Dascyleum is located on the southeast coast of Lake Manyas (Bandırma, Balıkesir/TURKEY). In addition to the settlement, Dascyleum has two necropolis areas in the east and south. These necropolis areas contain various types and sizes tombs, from different periods of Dascyleum. Among these tombs, the tomb which is defined as the Rock-cut Tomb II, consists of a long dro-mos and a burial chamber cut into the bedrock. During the excavations at the tomb in 2014, two klines carved into the bedrock with grave goods various types and forms has been revealed. The subject of the study is a dagger made of steel left as a grave good for the individual buried on one of these klines. Owing to the still in its sheath and well preserved in situ, this dagger serves as a rarely encountered archaeological find in terms of Anatolian and regional archeology. On the dagger that archaeometrically examined at the Ankara Hacı Bayram Veli University, Historical Material Conservation and Research Laboratory (MAKLAB), XRF, X-ray radiography, metallography, SEM-EDX and LIPS analyzes were performed. As a result of the data obtained from the analysis, informations about the chemical composition of the dagger, its production process and possible raw material source has been reached.

In central Russia, the examination of characteristics of economic activity of Bronze Age settlements and the determination of functional zones that existed in their territories in the first half of the second millennium BC based on the results of XRF (X-ray Fluorescence) analysis of samples of the cultural layer have never been done before. The data from elemental analysis of the samples of the cultural layer of the Bronze Age settlement Pesochnoe 1 from an excavation area of 126 m 2 obtained via the XRF method showed significant content of copper (Cu), zinc (Zn), calcium (Ca) and phosphorus (P), several times exceeding the content of the same chemical elements in the surrounding soils. The discovered Cu can be associated with metalworking, Zn are likely from ash and the biomass of the aquatic environment, and Ca and P can be found in bone remnants. Analysis of the spatial distribution of archaeological objects with quantitative indicators of Cu, Zn, Ca, P made it possible to distinguish two functional areas in the excavation of the Bronze Age settlement. A very high concentration of Cu, Zn, Ca, P recorded in the first functional zone, in the center of which was a hearth, indicates diverse activity that took place in this territory, including the use of different organic materials (plants, bones) as fuel and melting of metal. The second functional area with high concentrations of Zn, Ca and especially P suggests it was a place where biomaterials of animal origin might have been used.

The contribution discusses the results of the X-ray spectroscopy analyses performed on four solid-hilted bronze swords of the Early Iron Age Dolenjska group from southeastern Slovenia. One of them is the antennae sword from Podzemelj (8th century BC), which was found to be repaired at least twice before being placed into the grave of a prominent warrior. It originally had a rod tang that broke at some point and the blade was replaced. In contrast, the projection at the hilt terminal of the antennae sword from Vinji vrh (8th century BC) was cast together with the rest of the hilt and is not the tip of a rod tang. The sword from the River Sava at Krško is similar to the antennae swords from southeastern Europe of the 9th and 8th centuries in its bimetal composition. Its X-ray image indicates that the bronze hilt was cast onto the rod tang of the iron blade. The blade of the sword from Vir pri Stični (7th century BC) terminates at the lower part of the hilt, where it is attached with a pair of rivets to the handguard, while the three rivet holes in the grip section are empty, suggesting that the original blade was replaced with another one inserted only a few centimetres into the hilt. Such a sword was no longer suitable for chopping; it could rather be used for thrusting.

Variations of trace element (e.g. Mg, Sr, Ba, Fe, Zn etc.) concentrations along a speleothem's growth axis constitute important paleoclimate proxies. The use of laboratory micro X-ray fluorescence spectrometry as a fast and cheap alternative for conventional mass spectrometry techniques for trace element analysis on speleothems has been explored in the past and yielded satisfactory results. However, within the speleothem community there is need for an in-depth investigation of the full potential of this analytical technique. Compared to other types of paleoclimate archives, benchtop (μ)XRF analysis on speleothems is analytically more challenging because of the high-crystalline speleothem matrix and the low abundance of the elements of interest. In this study, several speleothem samples with differences in mineralogy (calcite versus aragonite) and composition are investigated. Various instrumental parameters are tested and recommendations are made for future studies applying (μ)XRF analysis to speleothems. Quantification based on a multiple standard calibration and an assessment of the error is carried out. Through validation with mass spectrometry techniques, it is confirmed that benchtop μXRF devises are able to generate speleothem trace element records. Successful results were obtained for Sr, Mg and Fe, while Zn and Ba were quantified in samples characterized by high concentrations. Nevertheless, caution has to be taken when interpreting the results, due to the presence of diffraction caused by the crystallinity of the samples. The elements which provide reliable results are sample specific and depend on the type of matrix and elemental abundance. These findings are applied on an Eemian to early Weichselian stalagmite from the Han-sur-Lesse Cave, Belgium. Time series were constructed for Mg and Sr, creating a multiproxy dataset together with previously obtained stable isotope (δ 13 C and δ 18 O) ratios, growth-rate and stalagmite morphology. It appears that Mg and Sr are not primarily controlled by prior calcite precipitation, but rather by changes in vegetation activity above the cave.