Metal Analysis

La fouille d'une longue structure excavée à Kergariou à Quimper (Finistère, France) a livré un important ensemble de bronzes comportant des haches à douille de type armoricain associées en particulier à des fragments de parures annulaires caractéristiques du Ha D. Une révision critique des associations des haches à douille de type armoricain en France amène à conclure que, dans l'état actuel de l'information, aucune ne provient d'un contexte antérieur au premier âge du Fer -plus précisément au Ha D -ni en Bretagne ou Normandie, ni ailleurs en France. Autrement dit, qu'il n'existe aucune association fiable de hache à douille de type armoricain avec un ensemble de l'horizon de l'épée en langue de carpe de la fin de l'âge du Bronze.

La fouille d'une longue structure excavée à Kergariou à Quimper (Finistère, France) a livré un important ensemble de bronzes comportant des haches à douille de type armoricain associées en particulier à des fragments de parures annulaires caractéristiques du Ha D. Une révision critique des associations des haches à douille de type armoricain en France amène à conclure que, dans l'état actuel de l'information, aucune ne provient d'un contexte antérieur au premier âge du Fer -plus précisément au Ha D -ni en Bretagne ou Normandie, ni ailleurs en France. Autrement dit, qu'il n'existe aucune association fiable de hache à douille de type armoricain avec un ensemble de l'horizon de l'épée en langue de carpe de la fin de l'âge du Bronze.

Germanium-on-insulator (GOI) is desired for high performance metal-oxide-semiconductor transistors and monolithically integrated optoelectronics. We demonstrate a promising approach to achieve single-crystal defect-free GOI by using lateral over-growth through SiO2 window. The dislocations due to the lattice mismatch are effectively terminated and reduced in SiO2 trench by selective area heteroepitaxy combined with hydrogen annealing. Low defect density of 4×106 cm−2 and low surface roughness of 0.7 nm (root-mean-square) on GOI are confirmed by plan-view transmission electron microscopy and atomic force microscopy analysis. In addition, the excellent metal-semiconductor-metal diode electrical characteristics fabricated on this GOI confirm Ge crystal quality. The selectively grown GOI structure can provide the monolithic integration of SiGe based devices on a Si very large scale integration (VLSI) platform.

Rapid, selective detection of metals in complex samples remains an elusive goal that could provide critical analytical information for biological and environmental sciences and industrial waste management. Fast-scan cyclic voltammetry (FSCV) using carbon-fiber microelectrodes (CFMs) is an emerging technique for metal analysis with broad potential applicability because of its rapid response to changes in analyte concentration and minimal disturbance to the analysis medium. In this communication, we report the first effective application of covalently modified CFMs to achieve highly selective, subsecond Cu(II) measurements using FSCV. A two-part strategy is employed for maximum selectivity: Cu(II) binding is augmented by a covalently grafted ionophore, while binding of other metals is prevented by chemical blocking of nonselective surface adsorption sites. The resulting electrodes selectively detect Cu(II) in a complex medium comprising several interfering metals. Overall, this strate...

This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier's archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright

Early Iron Age bronze socketed axes of the 
‘Armorican’ type are inspired by the Late Bronze
Age socketed axes and have previously been con
fused with them. However, they do not conform
to Late Bronze Age standards but are skeuo
morphic objects. Huge quantities of those axes
have been discovered in Brittany and Normandy,
where they were traditionally attributed to end
of the Late Bronze Age (Ha B2–B3) and thought
to have persisted throughout the Early Iron Age.
However, a critical review of alleged Late Bronze
Age hoards containing those axes proves this idea
wrong. Their contexts date to the Ha D phase, per
haps as early as Ha C. Both objects and contexts 
differ from their Late Bronze Age parallels and
hint at new concepts of metal use and circulation.
The deposition of Armorican socketed axes con
trasts with Late Bronze Age hoarding practices
and must be understood against a broader West
ern European context of transition. Hoards were
frequent during the Late Bronze Age, (nearly)
disappeared during the Ha C phase, and became
more frequent again during the Ha D phase. It is
argued that the Early Iron Age, the bronze sock
eted axes’ ‘uselessness’ is a key aspect to the un
derstanding of how their social role differs from
that of Late Bronze Age examples, but also of how
new standards were established during a period
of change. Often considered as evidence of conti
nuity, they might also inform us about how tradi
tional objects and practices were reused in new
scial contexts.
Carp’s Tongue sword phase; Early Iron Age; Hallstatt D

Germanium-on-insulator (GOI) is desired for high performance metal-oxide-semiconductor transistors and monolithically integrated optoelectronics. We demonstrate a promising approach to achieve single-crystal defect-free GOI by using lateral over-growth through SiO2 window. The dislocations due to the lattice mismatch are effectively terminated and reduced in SiO2 trench by selective area heteroepitaxy combined with hydrogen annealing. Low defect density of 4×106 cm−2 and low surface roughness of 0.7 nm (root-mean-square) on GOI are confirmed by plan-view transmission electron microscopy and atomic force microscopy analysis. In addition, the excellent metal-semiconductor-metal diode electrical characteristics fabricated on this GOI confirm Ge crystal quality. The selectively grown GOI structure can provide the monolithic integration of SiGe based devices on a Si very large scale integration (VLSI) platform.

Proximate composition and levels of metals in four commonly consumed species, Sonchus eruca, Melia azadirchta, Withania coagulans and Fagonia indica, were investigated for the first time. Ash, carbohydrate, protein, fiber, fat and moisture were arranged on dry basis, while Cu, Pb, Co, Cd, Fe, Cr, Mg and Na were also investigated in metal analysis using association of official analytical chemists (AOAC) methods and atomic absorption spectrometric techniques. However, M. azadirachta was found to be rich in fiber content and energy values. The results of metal analysis showed that M. azadirachta had the highest concentrations of the metals like Cu, Mn, Cr and Fe while S. eruca contain higher concentration of Na as compared to other three species.

The comparative study of glucose determination by selected point-of-care glucose meters on the quality control viewpoint STRESZCZENIE WSTĘP. Od momentu pojawienia się technik analitycznych, umożliwiających pozalaboratoryjne oznaczanie stężenia glukozy we krwi, w diagnostyce i terapii cukrzycy podkreśla się ich zalety, do których należą szybkość i łatwość wykonania pomiaru oraz możliwość otrzymania wyniku natychmiast. Jednak istnieją także pewne ograniczenia oraz potencjale źródła błędów, takie jak problemy z uzyskaniem odpowiedniej precyzji i dokładności w każdym wykonanym oznaczeniu. MATERIAŁ I METODY. Jako materiał badawczy wykorzystano modelowe roztwory wzorcowe, krew pełną oraz certyfikowane materiały odniesienia. Oznaczenie stężenia glukozy przeprowadzono za pomocą dostępnych na polskim rynku przenośnych analizatorów glukozy. WYNIKI. Otrzymane dane poddano analizie statystycznej. Porównano możliwości poszczególnych urządzeń pod kątem precyzji, dokładności i niepewności pomiarowej. WNIOSKI. Na podstawie badań własnych stwierdzono, że testowane urządzenia charakteryzują się sto-sunkowo dobrą precyzją, jednak wątpliwości budzi ich dokładność pomiarowa.

Depuis les années 1960, des objets en métal blanc, altérés et extrêmement friables, ont été mis au jour dans des sépultures de nécropoles à inhumation du 1er âge du Fer sur la Plaine de Caen (Calvados). Ils ont été à l’époque systématiquement qualifiés d’objets en « métal plombifère ».

Afin d’identifier plus précisément la nature de ces vestiges corrodés, de premières analyses chimiques ont été menées récemment sur quelques parures de deux de ces nécropoles. Elles ont permis de valider la nature du métal majoritaire : l’étain. En mars 2023, le projet Tin People a été alors lancé pour vérifier l’existence d’objets en étain dans d’autres tombes du 1er âge du Fer, mis au jour lors de fouilles récentes et plus anciennes en Normandie (10 nécropoles).

Ce poster présente les premiers résultats de la composition chimique du corpus d’objets en métal « plombifère », combinant analyses par fluorescence X portable (22 pièces) et par émission de rayons X incorporé à un microscope électronique à balayage (14 échantillons). Quatre groupes de composition ont été identifiés dont de l’étain pur et de l’étain allié au plomb. L’utilisation d’étain pur pour la fabrication de parures est à ce jour inédite et constitue une donnée de première importance sur les usages de l’étain à l’âge du Fer.

En croisant données archéologiques, anthropologiques des sujets porteur·euses et analyses chimiques, cette étude apporte des éléments nouveaux pour la compréhension de ces populations, qui se caractérisent par l’emploi de ce type de parures, pratique jusque-là inconnue en Europe.

The Akko 1 shipwreck was a small Egyptian armed vessel or auxiliary naval brig built in the eastern Mediterranean at the beginning of the 19th century. During the underwater excavations, about 230 brass hook-and-eye closures were found, mainly in the bow area. In addition, 158 brass cases were found, mainly between midships and the aft extremity of the shipwreck. Metallurgical non-destructive and destructive characterizations of selected items were performed, including radiographic testing, XRF, lead isotope analysis, optical microscopy, SEM-EDS and microhardness tests. The hook-and-eye closures and the cases were both found to be made of binary copper-zinc alloy (about 30 wt.% zinc). While the brass cases were made from rolled sheets, handmade using simple tools, and joined by tinlead soldering material, the brass hook-and-eye closures were handmade from drawn brass wire, and manufactured from commercial drawn brass bars by a cold-working process. The lead isotope analyses suggest different provenances of the raw materials used for making the brass objects, thus the different origins of the ores may hint that the brass wire and sheet were imported to the workshops in which the objects were manufactured.

A rare occasion to investigate the conservation mode of the heart of the philosopher Voltaire (1694-1778) presented itself following an incident with his statue at the National Library of France which enclosed the organ. A multidisciplinary study was carried out to propose and implement an improved reconditioning method for the organ. The study generated a better knowledge of the fabrication technique of funeral metallic boxes as well as a better understanding of the degradation process of both the organ and the box. The heart and its conditioning, as well as the volatile products (VOCs) released by the heart were analysed with nondestructive methods. X-ray fluorescence spectroscopy (XRF) and scanning electron microscopy associated with X-ray microanalysis (SEM-EDX) were used for the identification of the metal, the preparation and the gilding of the metal box. The heart-shaped metal box is made of lead with tin welds. The box received a double layer white lead preparation. The bind...

We report the results of an analytical investigation on 416 silver-copper coins stemming from the Ottoman Empire (end of 16th and beginning of 17th centuries), using synchrotron micro X-ray fluorescence analysis (SRXRF). In the past, analyses had already been conducted with energy dispersive X-ray fluorescence analysis (EDXRF), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM/EDX) and proton induced X-ray emission spec

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true-heart metal composition. m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy-dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred.

A rare occasion to investigate the conservation mode of the heart of the philosopher Voltaire (1694-1778) presented itself following an incident with his statue at the National Library of France which enclosed the organ. A multidisciplinary study was carried out to propose and implement an improved reconditioning method for the organ. The study generated a better knowledge of the fabrication technique of funeral metallic boxes as well as a better understanding of the degradation process of both the organ and the box. The heart and its conditioning, as well as the volatile products (VOCs) released by the heart were analysed with nondestructive methods. X-ray fluorescence spectroscopy (XRF) and scanning electron microscopy associated with X-ray microanalysis (SEM-EDX) were used for the identification of the metal, the preparation and the gilding of the metal box. The heart-shaped metal box is made of lead with tin welds. The box received a double layer white lead preparation. The binding of the preparation is probably of proteinic nature. Gold leaf had been deposited on a gilding bole made of a mixture of red ochre and minium, enhancing the preciousness of this particular artefact. Identification of VOCs released from the heart done by SPME fibres followed by gas chromatography-mass spectrometry (GC-MS) analysis confirmed the origin of the strong smell, essentially acetic acid. From the inside of the heart-shaped metal box, emission of VOCs suggest that the organ may have been embalmed in a liquid containing alcohol (spirit of wine), resins, natural extracts or essences from cedar or lavender. Histological analysis of tissue samples showed the presence of striated muscle fibres. These results helped to determine the optimal reconditioning of the heart. It has been decided to keep the organ inside its metal box in a stabilized environment with static anoxia, in order to preserve the heart for future generations while protecting the tissues against oxygen degradation for further investigations.

On a longtemps fait de l’Espagne la principale source de l’or en France à partir du XVIe siècle. Il est cependant désormais attesté que les Normands qui trafiquaient avec le Golfe de Guinée depuis les ports d’Honfleur, du Havre et de Rouen, pouvaient en rapporter en quantité : certaines années, c’était bien plus que le Portugal lui-même, pourtant officiellement possessionné en Afrique. Dès lors, il semble y avoir corrélation entre retour des navires et activité de la Monnaie de Rouen. Afin de mieux cerner le phénomène identifié dans des archives variées et complémentaires, les auteurs de cet article ont en outre initié un programme d’analyses élémentaires de pièces de monnaie afin de tenter de déterminer l’origine de l’or délivré en Normandie, particulièrement à Rouen.

The Akko 1 shipwreck was a small Egyptian armed vessel or auxiliary naval brig built in the eastern Mediterranean at the beginning of the 19th century. During the underwater excavations, about 230 brass hook-and-eye closures were found, mainly in the bow area. In addition, 158 brass cases were found, mainly between midships and the aft extremity of the shipwreck. Metallurgical non-destructive and destructive characterizations of selected items were performed, including radiographic testing, XRF, lead isotope analysis, optical microscopy, SEM-EDS and microhardness tests. The hook-and-eye closures and the cases were both found to be made of binary copper-zinc alloy (about 30 wt.% zinc). While the brass cases were made from rolled sheets, handmade using simple tools, and joined by tinlead soldering material, the brass hook-and-eye closures were handmade from drawn brass wire, and manufactured from commercial drawn brass bars by a cold-working process. The lead isotope analyses suggest different provenances of the raw materials used for making the brass objects, thus the different origins of the ores may hint that the brass wire and sheet were imported to the workshops in which the objects were manufactured.

Armorican-type socketed axes, particularly numerous in Brittany and Normandy, have been the subject of debate on both their purpose and their date since the 18th century. At the end of the 19th century, G. and A. de Mortillet claimed an Iron Age attribution for some medium-sized and miniature non-functional versions, whereas the Brandivy-type functional axes were still dated to the Late Bronze Age. It was however J. Dechelette’s point of view, confirmed by J. Briard in his famous book Les depots bretons et l’âge du Bronze atlantique published in Rennes in 1965, which prevailed until the end of the 20th century: these axes were attributed to the carp’s tongue sword horizon from the Late Atlantic Bronze Age 3 (i.e. BF IIIb = British LBA 3 = HaB2-3, around 950-800 BC). Even though J. Briard favoured a production of these axes mostly during the end of the Bronze Age, he also demonstrated that this production continued during the First Iron Age. This traditional point of view of a mostly...

Rapid, selective detection of metals in complex samples remains an elusive goal that could provide critical analytical information for biological and environmental sciences and industrial waste management. Fast-scan cyclic voltammetry (FSCV) using carbon-fiber microelectrodes (CFMs) is an emerging technique for metal analysis with broad potential applicability because of its rapid response to changes in analyte concentration and minimal disturbance to the analysis medium. In this communication, we report the first effective application of covalently modified CFMs to achieve highly selective, subsecond Cu(II) measurements using FSCV. A two-part strategy is employed for maximum selectivity: Cu(II) binding is augmented by a covalently grafted ionophore, while binding of other metals is prevented by chemical blocking of nonselective surface adsorption sites. The resulting electrodes selectively detect Cu(II) in a complex medium comprising several interfering metals. Overall, this strate...

Rapid, selective detection of metals in complex samples remains an elusive goal that could provide critical analytical information for biological and environmental sciences and industrial waste management. Fast-scan cyclic voltammetry (FSCV) using carbon-fiber microelectrodes (CFMs) is an emerging technique for metal analysis with broad potential applicability because of its rapid response to changes in analyte concentration and minimal disturbance to the analysis medium. In this communication, we report the first effective application of covalently modified CFMs to achieve highly selective, subsecond Cu(II) measurements using FSCV. A two-part strategy is employed for maximum selectivity: Cu(II) binding is augmented by a covalently grafted ionophore, while binding of other metals is prevented by chemical blocking of nonselective surface adsorption sites. The resulting electrodes selectively detect Cu(II) in a complex medium comprising several interfering metals. Overall, this strate...

Analyses chimiques des objets metalliques des depots terrestres du Bronze moyen et du Bronze final du nord-ouest de la France. Mise en evidence d'une chronologie basee sur des signatures identifiables. Resume Au Bronze moyen, l'Europe de l'ouest est divisee en aires culturelles definies par la distribution et d'objets manufactures semblables, dont les objets metalliques des depots terrestres. Le programme de recherche sur les compositions chimiques de ceux-ci vise a savoir si les sources des metaux peuvent etre identiques ou differents au sein de ces aires, et a terme sur l'ensemble du territoire. Pour ce faire, une approche statistique a ete privilegiee afin de travailler avec des lots representatifs et de minimiser les effets des inevitables variations. Six depots du BM2 de la zone atlantique (Bretagne, Normandie, Pays de la Loire) ont ete analyses par ICP-AES, totalisant 161 objets. Les transitions BM1/BM2 et BM2/BF1 ont pu etre observees en prenant en compte ...

This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier's archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright

Photons, electrons and protons beams applied to the scientific investigation of archaeological materials provide complementary information for characterising the state of preservation and the provenance of the objects. Investigations were carried out on medieval silver coins of the ''Friesacher Pfennig'' and the ''Tiroler Kreuzer'' from the Kunsthistorisches Museum Vienna and the Oesterreichische Nationalbank. Techniques employed were EDXRF, SEM/EDX and PIXE. By determining the trace elements of the alloys it was possible to assign coins to their mint. The results outline advantages and disadvantages of EDXRF, SEM/EDX and PIXE when applied to corroded objects.

The purpose of this article is to review and evaluate cloud point extraction of metals and its coupling to different contemporary instrumental methods of analysis. This review covers a selection of the literature published on this topic over the period mainly between 1997 and September 2005 (consisting of 50 publications). The current state of the art for CPE concerning metals and metal chelates is presented with special emphasis on the hyphenation of this interesting extraction=preconcentration approach mediated by surfactants to spectrophotometry, atomic spectroscopy and separation techniques. We present contemporary CPE developments concerning metal speciation and determination and their application to different environmental, clinical, geological and food samples. Strategies for method development as well as future perspectives are also covered.

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true-heart metal composition. m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy-dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred.

We report the results of an analytical investigation on 416 silver-copper coins stemming from the Ottoman Empire (end of 16th and beginning of 17th centuries), using synchrotron micro X-ray fluorescence analysis (SRXRF). In the past, analyses had already been conducted with energy dispersive X-ray fluorescence analysis (EDXRF), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM/EDX) and proton induced X-ray emission spec

h i g h l i g h t s Cu-based armour from Eastern Georgia (IeII century AD?): check authenticity. Conventional metallography combined with in situ and non-destructive investigations (ToF-ND). Suspicious points: Al in the alloy, as-cast microstructure, artificial patina.

Les haches à douilles de type armoricain: une production strictement de l'âge du Fer. Critique des sources documentaires afférant à leur chronologie Armorican type socketed axes: apurelyIron Age production. Critical analysis of the documentation on their chronology José GOMEZ de SOTO À la mémoire de Jacques Briard _______________________ Résumé Dès le XVIII e siècle, les haches à douille en bronze dites de type armoricain, particulièrement abondantes en Bretagne et en Normandie, ont fait l'objet de débats, tant quant à leur finalité qu'à leur datation. À la fin du XIX e siècle G. et A. de Mortillet affirmaient une datation à l'âge du Fer des modèles non fonctionnels de taille moyenne et miniature, les haches fonctionnelles du type de Brandivy restant attribuées au Bronze final. Mais c'est le point de vue de J. Déchelette qui l'emporta jusqu'à la fin du XX e siècle : ces haches étaient attribuée à l'horizon de l'épée en langue de carpe du Bronze final atlantique 3 (BF IIIb = LBA 3 britannique = Ha B2-3, env. 950 à 800 av. J.-C.), avec une perduration au cours du premier âge du Ferreconnue par J. Briard.Bien qu'il commençât à être remis en cause à la fin du XX e siècle, ce point de vue traditionnel persiste chez certains auteurs. Aussi, le présent article se propose-t-il de produire un dossier aussi complet que possible de la question. Les éléments démontrant une production de ces hachesau premier âge du Ferseulementsont indiscutables : sur le continent, aucune ne peut être datée antérieurement à la phase récente du premier âge du Fer(Ha D). L'actuelle « présence » de rares haches dans certains dépôts du BFa 3s'explique parleur pollution par des objets d'autres provenances, conséquences des aléas de leur conservation dans les collections et/ou les musées (ex., Plounéour-Lanvern, l'Île Verte, Aurigny). Parfois, quelques rassemblements d'objets aux provenances mal ou pas documentées réunis artificiellement ont été présentés commedesdépôts, lesquels n'avaient jamais existés (ex., Césarin). Dans d'autres cas, il s'agit d'une mélecture des sources documentaires (ex., Louvigné-du-Désert).Fait acquis essentiel, aucun dépôt de l'horizon de l'épée en langue de carpe, même parmi les plus volumineux (ex., Vénat, Jardin des Plantes, Prairie de Mauve, Belle Île), lorsqu'il est documenté de façon indiscutable, ne contient de hache à douille de type armoricain, aucune découverte récente non plus. Des prototypes des haches à douille de type armoricain abondaient dans les dépôts du Bronze final atlantique 3, dont quelques haches ornées de nervures verticales d'origine britannique ouapparentées pouvant annoncer celles du type de Brandivy et plus généralement, avec leurs décors de baguettes verticales, les autres modèles de haches à douille de type armoricain. Surtout, les haches du type du Plainseau préfigureraient celles dutype duTréhou et des types proches de Dahouët et de Plurien. Au début du premier âge du Fer, des haches font effectivement figures d'intermédiaires entre celles du type du Plainseau et celles de la famille Tréhou/Dahouët/Plurien(dépôt du Fossé Creuzette à Verberie). Les haches de petite taille des types de Maure, Saint-James et Couville, en revanche, ne possèdent pas de prototypes dans les dépôts de la fin de l'âge du Bronze. Il pourrait s'agir d'une production récente, la fin d'un processus d'évolution conduisant aux formes les moins fonctionnelles, que ne pas connaître leur finalité exacte peut nous faire considérer, au même titre que celles en plomb presque pur, comme les plus aberrantes de toutes. S'il estdésormais acquis que la production des haches à douille de type armoricain n'avait pas encore commencé pendant le Bronze final,la question du début de leur fabrication reste incertaine : leurvisibilité en Gaule se limite au Ha D.Que cette production ait pu débuter dès l'étape ancienne du premier âge du Fer(Ha C)ne demeure, en l'état actuel de l'information, qu'hypothèse, comme aussi d'ailleursune fin de production ou du moins de dépôt au début du second.La multiplication des dépôts de ces haches est surtout une des manifestations du phénomène général de reprise en Gaule des enfouissements de dépôts de métalau cours du Ha D, au même titre que, par exemple, les dépôts launaciens du Midi ou ceux de parures du Centre-Ouest et de la Loire moyenne. Mots clés Haches à douille de type armoricain, dépôts de bronze, parures, Bronze final atlantique 3, premier âge du Fer, Bretagne, Normandie Abstract (translated by E. Thauvin-Boulestin) The Armorican type socketed axes, particularly abounding in Brittany and Normandy, have been the subject of debates on both their purpose and their dating since the 18th century. At the end of the 19th century, G. and A. de Mortillet claimed an Iron Age attribution for some medium and miniature non-functional versions, whereas the Brandivy type functional axes were still dated to Late Bronze Age. Yet, this is J. Déchelette's point of view, confirmed by J. Briard in his famous book "Les dépôtsbretons et l'âge du Bronze atlantique" published in Rennes in 1965, which prevailed until the end of the 20th century: these axes were attributed to the carp's tongue sword horizon from Late Atlantic Bronze Age 3 (i.e. BFIIIb = British LBA 3 = HaB2-3, around 950-800 BC). Even though J. Briard favoured a production of theses axes mostly during the end of the Bronze Age, he also demonstrated that this production continued during the Early Iron Age. This traditional point of view of a mostly Late Bronze Age production began to be questioned at the end of the 20th century, even by J. Briard himself, nevertheless it still persists among some authors. The purpose of this article is thus to produce as comprehensive a file as possible on this issue. The elements testifying to a production of these axes exclusively during Early Iron Age are indisputable: on mainland Europe, no axe can today be dated for certain prior to HaD. The rare axes currently appearing in some Late Bronze Age 3 hoards can be explained by the "pollution" of these hoards with objects from other origins, as a consequence of hazardous conservation conditions in collections and/or museums (for instance Plounéour-Lanvern and l'ÎleVerte, Finistère; Durtal, Maine-et-Loire; Longy-Common, Aurigny). Sometimes, objects from non-or poorly documented origins have been artificially brought together and presented as hoards, although the latter never existed (for instance Césarin, Corrèze). In other cases, it comes from a misinterpretation of the documentary sources (e.g.Louvigné-du-Désert, Ille-et-Vilaine). It is a crucial established fact that no hoard from the carp's tongue sword horizon among those formerly discovered and indisputably documented, even the largest ones (for instance Vénat, Jardin des Plantes, Prairie de Mauve), has ever yielded an Armorican type socketed axe. The same applies to all the hoards discovered during the second half of the 20th century and the beginning of the 21th (for instance Gouesnac'h,

Proximate composition and levels of metals in four commonly consumed species, Sonchus eruca, Melia azadirchta, Withania coagulans and Fagonia indica, were investigated for the first time. Ash, carbohydrate, protein, fiber, fat and moisture were arranged on dry basis, while Cu, Pb, Co, Cd, Fe, Cr, Mg and Na were also investigated in metal analysis using association of official analytical chemists (AOAC) methods and atomic absorption spectrometric techniques. However, M. azadirachta was found to be rich in fiber content and energy values. The results of metal analysis showed that M. azadirachta had the highest concentrations of the metals like Cu, Mn, Cr and Fe while S. eruca contain higher concentration of Na as compared to other three species.

In general, feature points and camera parameters can only be estimated with limited accuracy due to noisy images. In case of collinear feature points, it is possible to benefit from this geometrical regularity by correcting the feature points to lie on the supporting estimated straight line, yielding increased accuracy of the estimated camera parameters. However, regarding Maximum-Likelihood (ML) estimation, this procedure is incomplete and suboptimal. An optimal solution must also determine the error covariance of corrected features. In this paper, a complete theoretical covariance propagation analysis starting from the error of the feature points up to the error of the estimated camera parameters is performed. Additionally, corresponding Fisher Information Matrices are determined and fundamental relationships between the number and distance of collinear points and corresponding error variances are revealed algebraically. To demonstrate the impact of collinearity, experiments are conducted with covariance propagation analyses, showing significant reduction of the error variances of the estimated parameters.

Rapid, selective detection of metals in complex samples remains an elusive goal that could provide critical analytical information for biological and environmental sciences and industrial waste management. Fast-scan cyclic voltammetry (FSCV) using carbon-fiber microelectrodes (CFMs) is an emerging technique for metal analysis with broad potential applicability because of its rapid response to changes in analyte concentration and minimal disturbance to the analysis medium. In this communication, we report the first effective application of covalently modified CFMs to achieve highly selective, subsecond Cu(II) measurements using FSCV. A two-part strategy is employed for maximum selectivity: Cu(II) binding is augmented by a covalently grafted ionophore, while binding of other metals is prevented by chemical blocking of nonselective surface adsorption sites. The resulting electrodes selectively detect Cu(II) in a complex medium comprising several interfering metals. Overall, this strate...

Les haches à douilles de type armoricain: une production strictement de l'âge du Fer. Critique des sources documentaires afférant à leur chronologie Armorican type socketed axes: apurelyIron Age production. Critical analysis of the documentation on their chronology José GOMEZ de SOTO À la mémoire de Jacques Briard _______________________ Résumé Dès le XVIII e siècle, les haches à douille en bronze dites de type armoricain, particulièrement abondantes en Bretagne et en Normandie, ont fait l'objet de débats, tant quant à leur finalité qu'à leur datation. À la fin du XIX e siècle G. et A. de Mortillet affirmaient une datation à l'âge du Fer des modèles non fonctionnels de taille moyenne et miniature, les haches fonctionnelles du type de Brandivy restant attribuées au Bronze final. Mais c'est le point de vue de J. Déchelette qui l'emporta jusqu'à la fin du XX e siècle : ces haches étaient attribuée à l'horizon de l'épée en langue de carpe du Bronze final atlantique 3 (BF IIIb = LBA 3 britannique = Ha B2-3, env. 950 à 800 av. J.-C.), avec une perduration au cours du premier âge du Ferreconnue par J. Briard.Bien qu'il commençât à être remis en cause à la fin du XX e siècle, ce point de vue traditionnel persiste chez certains auteurs. Aussi, le présent article se propose-t-il de produire un dossier aussi complet que possible de la question. Les éléments démontrant une production de ces hachesau premier âge du Ferseulementsont indiscutables : sur le continent, aucune ne peut être datée antérieurement à la phase récente du premier âge du Fer(Ha D). L'actuelle « présence » de rares haches dans certains dépôts du BFa 3s'explique parleur pollution par des objets d'autres provenances, conséquences des aléas de leur conservation dans les collections et/ou les musées (ex., Plounéour-Lanvern, l'Île Verte, Aurigny). Parfois, quelques rassemblements d'objets aux provenances mal ou pas documentées réunis artificiellement ont été présentés commedesdépôts, lesquels n'avaient jamais existés (ex., Césarin). Dans d'autres cas, il s'agit d'une mélecture des sources documentaires (ex., Louvigné-du-Désert).Fait acquis essentiel, aucun dépôt de l'horizon de l'épée en langue de carpe, même parmi les plus volumineux (ex., Vénat, Jardin des Plantes, Prairie de Mauve, Belle Île), lorsqu'il est documenté de façon indiscutable, ne contient de hache à douille de type armoricain, aucune découverte récente non plus. Des prototypes des haches à douille de type armoricain abondaient dans les dépôts du Bronze final atlantique 3, dont quelques haches ornées de nervures verticales d'origine britannique ouapparentées pouvant annoncer celles du type de Brandivy et plus généralement, avec leurs décors de baguettes verticales, les autres modèles de haches à douille de type armoricain. Surtout, les haches du type du Plainseau préfigureraient celles dutype duTréhou et des types proches de Dahouët et de Plurien. Au début du premier âge du Fer, des haches font effectivement figures d'intermédiaires entre celles du type du Plainseau et celles de la famille Tréhou/Dahouët/Plurien(dépôt du Fossé Creuzette à Verberie). Les haches de petite taille des types de Maure, Saint-James et Couville, en revanche, ne possèdent pas de prototypes dans les dépôts de la fin de l'âge du Bronze. Il pourrait s'agir d'une production récente, la fin d'un processus d'évolution conduisant aux formes les moins fonctionnelles, que ne pas connaître leur finalité exacte peut nous faire considérer, au même titre que celles en plomb presque pur, comme les plus aberrantes de toutes. S'il estdésormais acquis que la production des haches à douille de type armoricain n'avait pas encore commencé pendant le Bronze final,la question du début de leur fabrication reste incertaine : leurvisibilité en Gaule se limite au Ha D.Que cette production ait pu débuter dès l'étape ancienne du premier âge du Fer(Ha C)ne demeure, en l'état actuel de l'information, qu'hypothèse, comme aussi d'ailleursune fin de production ou du moins de dépôt au début du second.La multiplication des dépôts de ces haches est surtout une des manifestations du phénomène général de reprise en Gaule des enfouissements de dépôts de métalau cours du Ha D, au même titre que, par exemple, les dépôts launaciens du Midi ou ceux de parures du Centre-Ouest et de la Loire moyenne. Mots clés Haches à douille de type armoricain, dépôts de bronze, parures, Bronze final atlantique 3, premier âge du Fer, Bretagne, Normandie Abstract (translated by E. Thauvin-Boulestin) The Armorican type socketed axes, particularly abounding in Brittany and Normandy, have been the subject of debates on both their purpose and their dating since the 18th century. At the end of the 19th century, G. and A. de Mortillet claimed an Iron Age attribution for some medium and miniature non-functional versions, whereas the Brandivy type functional axes were still dated to Late Bronze Age. Yet, this is J. Déchelette's point of view, confirmed by J. Briard in his famous book "Les dépôtsbretons et l'âge du Bronze atlantique" published in Rennes in 1965, which prevailed until the end of the 20th century: these axes were attributed to the carp's tongue sword horizon from Late Atlantic Bronze Age 3 (i.e. BFIIIb = British LBA 3 = HaB2-3, around 950-800 BC). Even though J. Briard favoured a production of theses axes mostly during the end of the Bronze Age, he also demonstrated that this production continued during the Early Iron Age. This traditional point of view of a mostly Late Bronze Age production began to be questioned at the end of the 20th century, even by J. Briard himself, nevertheless it still persists among some authors. The purpose of this article is thus to produce as comprehensive a file as possible on this issue. The elements testifying to a production of these axes exclusively during Early Iron Age are indisputable: on mainland Europe, no axe can today be dated for certain prior to HaD. The rare axes currently appearing in some Late Bronze Age 3 hoards can be explained by the "pollution" of these hoards with objects from other origins, as a consequence of hazardous conservation conditions in collections and/or museums (for instance Plounéour-Lanvern and l'ÎleVerte, Finistère; Durtal, Maine-et-Loire; Longy-Common, Aurigny). Sometimes, objects from non-or poorly documented origins have been artificially brought together and presented as hoards, although the latter never existed (for instance Césarin, Corrèze). In other cases, it comes from a misinterpretation of the documentary sources (e.g.Louvigné-du-Désert, Ille-et-Vilaine). It is a crucial established fact that no hoard from the carp's tongue sword horizon among those formerly discovered and indisputably documented, even the largest ones (for instance Vénat, Jardin des Plantes, Prairie de Mauve), has ever yielded an Armorican type socketed axe. The same applies to all the hoards discovered during the second half of the 20th century and the beginning of the 21th (for instance Gouesnac'h,

The Saint-Blaise/Bains des Dames stratified site in Neuchâtel, Switzerland, contains several occupations that span the Late through Final Neolithic, including the Horgen, Lüscherz, and Auvernier-Cordé periods. As part of a study on prehistoric metallurgy in western Switzerland, we compare the lead isotope ratios (multicollector inductively coupled plasma mass spectrometer) and elemental compositions (instrumental neutron activation analysis) of the site's numerous copper finds to a database of corresponding measurements for copper ores throughout Europe. The results show a considerable variation in copper compositions present at the site, suggesting complex economic relationships and multiple chaînes opératoires during the time in question. Specifically, during the Final Neolithic, we distinguished ten coherent clusters, confirmed by both the elemental compositions and lead isotope ratios. When compared to the Europe-wide database of copper ores, we observed significant changes in the provenance of the copper through time that reflect equally significant changes in social, cultural, and economic interactions.

Proximate composition and levels of metals in four commonly consumed species, Sonchus eruca, Melia azadirchta, Withania coagulans and Fagonia indica, were investigated for the first time. Ash, carbohydrate, protein, fiber, fat and moisture were arranged on dry basis, while Cu, Pb, Co, Cd, Fe, Cr, Mg and Na were also investigated in metal analysis using association of official analytical chemists (AOAC) methods and atomic absorption spectrometric techniques. However, M. azadirachta was found to be rich in fiber content and energy values. The results of metal analysis showed that M. azadirachta had the highest concentrations of the metals like Cu, Mn, Cr and Fe while S. eruca contain higher concentration of Na as compared to other three species.

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true-heart metal composition. m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy-dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred.

Inhabitants of Tank and South Waziristan area of Pakistan are facing acute shortage of medicines and food. The purpose of this study was to evaluate the medicinal plants of the area for their nutrient and medicinal values and to recommend their preservation/propagation for medicinal and/or food purposes. The plants investigated were Alhagi maurorum Medik, Datura alba Ness, Chenopodium album L. Tecomella undulata (Sm.), Withania coagulans Dunal, Berberis lycium Royle. Proximate parameters like protein, fat, fiber, carbohydrates, moisture contents, ash, and energy values were obtained using Association of Official Analytical Chemists (AOAC) methods. Macronutrients (Ca, Mg, Na, and K) and micronutrients (Fe, Cu, Zn, Cr, Cd, Pb, and Ni) were analyzed by employing atomic absorption spectrophotometer. The study showed that Datura album has higher nutrient value than Withania coagulans and there exist a significant correlation among the results. Further, the plants were found to be useful for medicine and food purpose.

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true-heart metal composition. m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy-dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the m-synchrotron micro X-ray fluorescence analysis and m-proton-induced X-ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred.

La couleur d'un objet métallique peut être modifiée par un traitement chimique approprié qui en provoquant une transformation de la surface crée une couche superficielle ou patine intentionnelle. Ce procédé connu dans l'Egypte antique est repris par le monde Egéen, Romain puis au Japon au 14 e siècle. Les patines obtenues par ce procédé ne sont de couleur noire et bien adhérente uniquement sur les alliages de cuivre contenant de l'or et/ou de l'argent. En l'absence de métaux nobles la patine est rouge et très peu adhérente. Les microanalyses et la diffraction des rayons X ont montré que ces patines étaient toutes formées de cuprite (Cu 2 O). Nous présentons ici les résultats de l'étude par microscopie électronique en transmission réalisée afin de préciser le rôle des métaux nobles. La difficulté d'obtenir des coupes transverses de bonne qualité par une méthode classique a conduit à préparer les échantillons par FIB. Différentes techniques de découpe de membrane ont été testées. Les premiers résultats des observations MET seront exposés.

Proximate composition and levels of metals in four commonly consumed species, Sonchus eruca, Melia azadirchta, Withania coagulans and Fagonia indica, were investigated for the first time. Ash, carbohydrate, protein, fiber, fat and moisture were arranged on dry basis, while Cu, Pb, Co, Cd, Fe, Cr, Mg and Na were also investigated in metal analysis using association of official analytical chemists (AOAC) methods and atomic absorption spectrometric techniques. However, M. azadirachta was found to be rich in fiber content and energy values. The results of metal analysis showed that M. azadirachta had the highest concentrations of the metals like Cu, Mn, Cr and Fe while S. eruca contain higher concentration of Na as compared to other three species.

Arsenic, lin, lead and zinc are the principal elements used in copper-alloys of Middle East objects from the IVth and IIIrd millennia. On the basis of analytical results from the Laboratoire de Recherches des Musées de France and from the works of the R.C.P. 442 of the C.N.R.S., the evolution of the alloying technique has been demonstrated to occur discontinuously and differently from one region to another. Natural ressources, trade, technology, local particularisms, social structures allow to explain the main patterns of this complex evolution. Résumé L'arsenic, l'étain, le plomb et le zinc sont les principaux éléments que l'on trouve alliés au cuivre dans les objets moyen-orientaux des ive et ine millénaires. Sur la base des résultats analytiques acquis au Laboratoire de Recherche des Musées de France et au cours des travaux de la R.C.P. 442 du C.N.R.S.. l'évolution de la technique des alliages apparaît s'effectuer de manière discontinue et variable d'une région à l'autre. Ressources naturelles, commerce, technologie, particularismes locaux, types de société permettent d'expliquer dans les grandes lignes la complexité de cette évolution.