Local matters : pottery production at Tell Halaf and Tell Tawila

Los fragmentos cerámicos de los periodos Halaf y Ubaid de Tell Halaf, Tell Tawilla y de la región de Tell Chuera han sido analizados utilizando métodos geoquímicos, mineralógicos y petrográficos. El intercambio y las importaciones ceràmicas seran discutidos y los fragmentos cerámicos Samarra de Tell Halaf se podran associar a producciones principamente locales.Sherds of the Halaf and Ubaid periods from Tell Halaf, Tell Tawila and Chuera region were analysed through geochemical and mineralogical/petrographical methods. Pottery exchange and imports will be discussed and Samarra-like sherds

Metasomatic Replacement of Albite in Nature and Experiments

Replacement of albite by sodium-rich, secondary phases is a common phenomenon, observed in different geological settings and commonly attributed to alkaline metasomatism. We investigated growth of nepheline and sodalite on albite in time series experiments between two and 14 days. A total of 42 hydrothermal experiments were performed in cold-seal hydrothermal vessels at a constant pressure of 4 kbar and 200–800 °C in the system SiO2–Al2O3–NaCl–H2O. To allow for fluid flow and material transport, a double-capsule technique was used; hereby, a perforated inner Pt capsule was filled with cleavage fragments of natural albite, whereas the shut outer Au capsule was filled with γ-Al2O3 and the NaCl–H2O solution. Complete overgrowth of albite by sodalite and nepheline occurred after just two days of experiments. At high salinity (≥17 wt % NaCl) sodalite is the stable reaction product over the whole temperature range whereas nepheline occurs at a lower relative bulk salinity than sodalite and is restricted to a high temperature of ≥700 °C. The transformation of albite starts along its grain margins, cracks or twin lamellae. Along the reaction front sodalite crystallizes as small euhedral and highly porous grains forming polycrystalline aggregates. Coarse sodalite dominates in the outermost domains of the reaction zones, suggesting recrystallization. Sodalite may contain fluid inclusions with trapped NaCl-rich brine, demonstrating that the interconnected microporosity provides excellent pathways for fluid-assisted material transport. Highly porous nepheline forms large, euhedral crystals with rectangular outline. Sodalite and nepheline in natural rock samples display only minor porosity but fluid and secondary mineral inclusions, pointing to coarsening of a previously present microporosity. The reaction interface between sodalite and albite in natural rock samples is marked by open channels in transmission electron microscopy. In many of the experiments, a zone of Si–H-rich, amorphous material is developed at the reaction front, which occurs at a temperature of up to of 750 °C as nanometer to 350 µm wide reaction zone around albite. This change in composition corresponds with the abrupt termination of the crystalline feldspar structure. The presence of sodalite as micro- to nanometer-sized, euhedral crystals within the amorphous zone demonstrates, that both the sodalite reaction rim and the amorphous material allow for fluid-assisted material transport between the crystalline albite (release of Si, Al) and the bulk fluid (H2O, Na, Cl). This texture, moreover, suggests that the amorphous phase represents a metastable interstage reaction product, which is progressively replaced by sodalite and nepheline. Remarkably, product sodalite, nepheline, and the amorphous material largely inherit the trace element budget of the respective ancestor albite, indicating that at least part of the trace elements remained fixed during the reaction process. The observed reaction textures in both natural and experimental samples indicate an interfacial dissolution–reprecipitation mechanism. Results of our study bear important implications with respect to mineral replacement in the presence of a fluid phase, especially regarding the interpretation of trace element patterns of the product phases

Analysis of red chalk drawings from the workshop of Giovanni Battista Piranesi using fiber optics reflectance spectroscopy

The viability of fiber optics reflectance spectroscopy (FORS) for the differentiation of red chalk drawing media was investigated, focusing on the group of drawings from the workshop of Giovanni Battista Piranesi (1720–1778) at the Staatliche Kunsthalle Karlsruhe, Germany. The evaluation of spectra was supported by principal component analysis (PCA). The method was tested on mock-up drawings made with recently acquired natural and synthetic red chalks of known origin. It was possible to sort these mock-up drawings according to chalk type and application technique. The compositional differences of these reference chalks were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Subsequent FORS analysis of selected original drawings revealed the existence of several closely grouped clusters, implying similarities on the basis of the underlying spectral features among the historical red chalks used in Rome. These similarities distinguished the historical drawings from the red chalk mock-up drawings, except for the drawings made with red chalk samples from the area near the town of Theley, Germany, which were shown to bear close similarities to those in the cluster of historical samples

Correction to: Flow-through experiments on the interaction of sandstone with Ba-rich fluids at geothermal conditions

Abstract After publication of the article (Orywall et al. 2017), it has been brought to our attention that there are a number of errors. The authors have listed them below

II Workshop on Late Neolithic Ceramics in Ancient Mesopotamia : pottery in context

Aquest volum és el resultat del workshop celebrat per investigadors i especialistes en ceràmiques del Pròxim Orient que va tenir lloc al MAC-Empúries l'octubre de 2015. Els articles compilats en el llibre han estat escrits per 31 investigadors de 13 nacionalitats diferents i abasten temàtiques diverses al voltant de la producció ceràmica: matèries primeres, tècniques, analítiques, etc. Pel que fa al context geogràfic, els estudis se centren a Turquia, Siria, Irak, Jordània, Israel i Palestina, els països en que va aparèixer la ceràmica per primera vegada en l'àrea mediterrània, i on va experimentar un ràpid procés de transformació morfotipològic i tecnològic

Petrogenese der mesoproterozoischen Anorthosite, Syenite und Karbonatite NW-Namibias und ihr Einfluss auf die metasomatische Bildung der Sodalith-Vorkommen von Swartbooisdrif

During the Mesoproterozoic large volumes of magma were repeatedly emplaced within the basement of NW Namibia. Magmatic activity started with the intrusion of the anorthositic rocks of the Kunene Intrusive Complex (KIC) at 1,385-1,347 Ma. At its south-eastern margin the KIC was invaded by syenite dykes (1,380-1,340 Ma) and younger carbonatites (1,140-1,120 Ma) along ENE and SE trending faults. Older ferrocarbonatite intrusions, the ‘carbonatitic breccia’, frequently contain wallrock fragments, whereas subordinate ferrocarbonatite veins are almost xenolith-free. Metasomatic interaction between carbonatite-derived fluids and the neighbouring and incorporated anorthosites led to the formation of economically important sodalite deposits. Investigated anorthosite samples display the magmatic mineral assemblage of Pl (An37-75) ± Ol ± Opx ± Cpx + Ilm + Mag + Ap ± Zrn. Ilmenite and pyroxene are surrounded by narrow reaction rims of biotite and pargasite. During the subsolidus stage sporadic coronitic garnet-orthopyroxene-quartz assemblages were produced. Thermobarometry studies on amphiboles yield temperatures of 985-950°C whereas the chemical composition of coronitic garnet and orthopyroxene indicate a subsolidus re-equilibration of the KIC at conditions of 760 ± 100°C and 7.3 ± 1 kbar. In the syenites Kfs, Pl, Hbl and/or Cpx crystallized first, followed by a second generation of Kfs, Hbl, Fe-Ti oxides and Ttn. Crystallization of potassium feldspar occurred under temperatures of 890-790°C. For the crystallization of hastingsite pressures of 6.5 ± 0.6 kbar are obtained. In order to constrain the source rocks of the two suites, oxygen isotope analyses of feldspar as well as geochemical bulk rock analyses were carried out. In case of the anorthosites, the general geochemical characteristics are in excellent agreement with their derivation from fractionated basaltic liquids, with the d18O values (5.88 ± 0.19 ‰) proving their derivation from mantle-derived magmas. The results obtained for the felsic suite, provide evidence against consanguinity of the anorthosites and the syenites, i.e. (1) compositional gaps between the geochemical data of the two suites, (2) trace element data of the felsic suite points to a mixed crustal-mantle source, (3) syenites do not exhibit ubiquitous negative Eu-anomalies in their REE patterns, which would be expected from fractionation products of melts that previously formed plagioclase cumulates and (4) feldspar d18O values from the syenites fall in a range of 7.20-7.92 ‰, which, however, is about 1.6 ‰ higher than the average d18O of the anorthosites. Conformably, the crustal-derived felsic and the mantle-derived anorthositic suite are suggested to be coeval but not consanguineous. Their spatial and temporal association can be accounted for, if the heat necessary for crustal melting is provided by the upwelling and emplacement of mantle-derived melts, parental to the anorthosites. In order to constrain the source of the 1,140-1,120 Ma carbonatites and to elucidate the fenitizing processes, which led to the formation of the sodalite, detailed mineralogical and geochemical investigations, stable isotope (C,O,S) analyses and fluid inclusion measurements (microthermometrical studies and synchrotron-micro-XRF analyses) have been combined. There is striking evidence that carbonatites of both generations are magmatic in origin. They occur as dykes with cross-cutting relationships and margins disturbed by fenitic aureoles, and contain abundant flow-oriented xenoliths. The mineral assemblage of both carbonatite generations of Ank + Cal + Ilm + Mag + Bt ± Ap ± pyrochlore ± sulphides in the main carbonatite body and Ank + Cal + Mag ± pyrochlore ± rutile in the ferrocarbonatite veins, their geochemical characteristics and the O and C isotope values of ankerite (8.91 to 9.73 and –6.73 to –6.98, respectively) again indicate igneous derivation, with the 18O values suggesting minor subsolidus alteration. NaCl-rich fluids, released from the carbonatite melt mainly caused the fenitization of both, the incorporated and the bordering anorthosite. This process is characterized by the progressive transformation of Ca-rich plagioclase into albite and sodalite. Applying conventional geothermobarometry combined with fluid-inclusion isochore data, it was possible to reconstruct the P-T conditions for the carbonatite emplacement and crystallization (1200-630°C, 4-5 kbar) and for several mineral-forming processes during metasomatism (e.g. formation of sodalite: 800-530°C). The composition and evolutionary trends of the fenitizing solution were estimated from both the sequence of metasomatic reactions within wallrock xenoliths in the carbonatitic breccia and fluid inclusion data. The fenitizing solutions responsible for the transformation of albite into sodalite can be characterised as of NaCl-rich aqueous brines (19-30 wt.% NaCl eq.), that contained only minor amounts of Sr, Ba, Fe, Nb, and LREE.Die mesoproterozoische Entwicklung Namibias ist durch wiederholte magmatische Aktivität gekennzeichnet. Zunächst erfolgte vor 1385-1347 Ma die Platznahme von Anorthositen des Kunene-Intrusiv-Komplexes (KIK) innerhalb von hochgradig metamorphen Gesteinen des Epupa-Komplexes. Der KIK wurde nahe seiner südöstlichen Begrenzung von zahlreichen Störungen durchschlagen. In diese SE-NW und ENE-WSW streichenden Schwächezonen intrudierten Syenite (ca. 1380-1340 Ma) sowie jüngere Karbonatite (ca. 1140-1120 Ma). Hierbei erfolgte zunächst die Platznahme einer ersten Ferrokarbonatit-Generation, die in hohem Maße durch Anorthosit-Xenolithe kontaminiert ist („karbonatitische Brekzie“). Diese wird von jüngeren und annähernd Xenolith-freien Ferrokarbonatit-Adern durchschlagen. Metasomatische Wechselwirkungen den Karbonatit-Magmen und angrenzenden Anorthositen und Anorthosit-Xenolithen führten zur Bildung ökonomisch bedeutsamer Sodalith-Vorkommen. Die typische primär-magmatische Mineralogie in den Gesteinen des KIK umfasst: Pl (An37-75) ± Ol ± Opx ± Cpx + Fe-Ti-Oxide + Ap ± Zrn. Säume von Amphibol und Biotit umgeben Pyroxen und Ilmenit. Geothermometrische Untersuchungen ergaben Temperaturen von 985-950°C für die Kristallisation von Amphibol. Eine Reequilibrierung der Anorthosite unter granulit- bis amphibolitfaziellen Bedingungen (760 ± 100°C; 7.3 ± 1 kbar) wurde für Orthopyroxen-Granat-Quarz-Koronen um Olivin festgestellt. In den Syeniten kristallisierten zunächst Kfs, Pl, Cpx und Hbl, gefolgt von einer zweiten Generation von Kfs, Hbl, Fe-Ti-Oxiden und Ttn. Die Kristallisation von K-Feldspat fand unter Temperaturbedingungen von 890-790°C statt. Für die Kristallisation von Hastingsit wurden Drucke von 6.5 ± 0.6 kbar ermittelt. Mit dem Ziel, die Natur der Magmenquelle der Anorthosite und Syenite zu charakterisieren wurden geochemische Untersuchungen durchgeführt, sowie die Sauerstoff-Isotopie von Feldspat-Separaten bestimmt. Die Ergebnisse dieser Untersuchungen belegen, dass es sich bei den Stamm-Magmen der Anorthosite um fraktionierte basaltische Magmen handelt. Die d18O-Daten (5.61-6.13 ‰) legen nahe, dass diese Schmelzen durch partielle Aufschmelzung des Erdmantels entstanden sind. Die für die Syenite ermittelten Ergebnisse belegen, dass es sich bei Anorthositen und Syeniten um chemisch unabhängige Systeme handelt, da (1) keine chemische Kontinuität zwischen Anorthositen und Syeniten vorliegt, (2) die Spurenelementgehalte der Syenite auf eine gemischte Kruste-Mantel-Quelle hindeuten, (3) Chondrit-normierte Seltenerd-Element-Muster der Syenite keine negative Eu-Anomalie aufweisen, und (4) die d18O-Werte von Feldspat der Syenite mit 7.20-7.92 ‰ etwa 1.6 ‰ höher liegen als die der Anorthosite. Dementsprechend liegt die enge räumliche und zeitliche Assoziation von Anorthosite und Syeniten vermutlich darin begründet, dass der Aufstieg und die Platznahme der Stamm-Magmen der Anorthosite zum partiellen Aufschmelzen der Unterkruste und somit zur Bildung potentieller Stamm-Magmen der Syenite führten. Um eine umfassende Vorstellung über die genetische und zeitliche Stellung der Karbonatite und über die Sodalith-bildenden Vorgänge zu gewinnen, wurden verschiedene Untersuchungsmethoden angewendet (petrographische und Mikrosonden-analytische Bearbeitung von Dünnschliffen, Bestimmung der Gesamtgesteins-Geochemie, mikrothermometrische Untersuchungen sowie Synchrotron-XRF(SRXRF)-Untersuchungen von Fluid-Einschlüssen, Laser-ICPMS und SRXRF-Analysen der Spurenelement-Gehalte ausgesuchter Minerale sowie O-, C- und S-Isotopenanalytik). Die für die Karbonatite gewonnenen Ergebnisse belegen eindeutig, dass es sich hierbei um magmatische Kristallisationsprodukte fraktionierter Mantelschmelzen darstellen: Die Karbonatite treten als Gänge auf, welche ältere Gesteinseinheiten durchschlagen. Gesteine im Kontakt zu den Karbonatiten haben eine metasomatische Überprägung erfahren; Nebengesteinsklasten werden von Karbonat-reichen Lagen umflossen. Die Mineralogie beider Karbonatit-Generationen, i.e. (1) Ank + Cal + Mag + Bt ± Ilm ± Ap ± Pyrochlor ± Sulfide in der karbonatitischen Brekzie und (2) Ank + Cal + Mag ± Pyrochlor ± Rutil der Ferrokarbonatit-Adern, ihre geochemischen Signaturen sowie die O- und C-Isotopie von Ankerit (8.91-9.73 ‰ d18O und –6.73 bis –6.98 ‰ d13C) bestätigen diese Interpretation, wobei die O-Isotopendaten eine schwache hydrothermale Alteration der Karbonatite nahe legen. Die Ergebnisse von konventioneller Geothermometrie in Kombination mit den für Fluid-Einschlüsse kalkulierten Isochoren belegen, dass die Platznahme der Karbonatite unter P-T-Bedingungen von 4-5 kbar und 1200-630°C erfolgte. Unter Temperaturen von 800-530°C bewirkte die Zirkulation NaCl-reicher wässriger Fluide (19-30 Gew.% NaCl äquivalent) die Umwandlung von Albit der eingeschlossenen Anorthosit-Bruchstücke in Sodalith. Wie SRXRF-Analysen belegen, enthielten die fenitisierenden Fluide zudem geringe Konzentrationen an Sr, Ba, Fe, Nb und SEE

Metasomatic Replacement of Albite in Nature and Experiments

Replacement of albite by sodium-rich, secondary phases is a common phenomenon, observed in different geological settings and commonly attributed to alkaline metasomatism. We investigated growth of nepheline and sodalite on albite in time series experiments between two and 14 days. A total of 42 hydrothermal experiments were performed in cold-seal hydrothermal vessels at a constant pressure of 4 kbar and 200–800 °C in the system SiO2–Al2O3–NaCl–H2O. To allow for fluid flow and material transport, a double-capsule technique was used; hereby, a perforated inner Pt capsule was filled with cleavage fragments of natural albite, whereas the shut outer Au capsule was filled with γ-Al2O3 and the NaCl–H2O solution. Complete overgrowth of albite by sodalite and nepheline occurred after just two days of experiments. At high salinity (≥17 wt % NaCl) sodalite is the stable reaction product over the whole temperature range whereas nepheline occurs at a lower relative bulk salinity than sodalite and is restricted to a high temperature of ≥700 °C. The transformation of albite starts along its grain margins, cracks or twin lamellae. Along the reaction front sodalite crystallizes as small euhedral and highly porous grains forming polycrystalline aggregates. Coarse sodalite dominates in the outermost domains of the reaction zones, suggesting recrystallization. Sodalite may contain fluid inclusions with trapped NaCl-rich brine, demonstrating that the interconnected microporosity provides excellent pathways for fluid-assisted material transport. Highly porous nepheline forms large, euhedral crystals with rectangular outline. Sodalite and nepheline in natural rock samples display only minor porosity but fluid and secondary mineral inclusions, pointing to coarsening of a previously present microporosity. The reaction interface between sodalite and albite in natural rock samples is marked by open channels in transmission electron microscopy. In many of the experiments, a zone of Si–H-rich, amorphous material is developed at the reaction front, which occurs at a temperature of up to of 750 °C as nanometer to 350 µm wide reaction zone around albite. This change in composition corresponds with the abrupt termination of the crystalline feldspar structure. The presence of sodalite as micro- to nanometer-sized, euhedral crystals within the amorphous zone demonstrates, that both the sodalite reaction rim and the amorphous material allow for fluid-assisted material transport between the crystalline albite (release of Si, Al) and the bulk fluid (H2O, Na, Cl). This texture, moreover, suggests that the amorphous phase represents a metastable interstage reaction product, which is progressively replaced by sodalite and nepheline. Remarkably, product sodalite, nepheline, and the amorphous material largely inherit the trace element budget of the respective ancestor albite, indicating that at least part of the trace elements remained fixed during the reaction process. The observed reaction textures in both natural and experimental samples indicate an interfacial dissolution–reprecipitation mechanism. Results of our study bear important implications with respect to mineral replacement in the presence of a fluid phase, especially regarding the interpretation of trace element patterns of the product phases

Correction to: Flow-through experiments on the interaction of sandstone with Ba-rich fluids at geothermal conditions

Abstract After publication of the article (Orywall et al. 2017), it has been brought to our attention that there are a number of errors. The authors have listed them below