A Great Big Melting Pot: Exploring Patterns of Glass Supply,Consumption and Recycling in Roman Coppergate,York*

One hundred and ninety three glass fragments from the canabae in York were analysed (first to fourth centuries). They fall into six compositional groups: antimony colourless (Sb), high‐manganese (high‐Mn), low‐manganese (low‐Mn), mixed antimony and manganese (Sb–Mn), high iron, manganese and titanium (HIMT) and plant ash. Some groups represent production groups, some of which appear to be in limited supply in this western outpost, but are more prevalent elsewhere, and others reflect changing supply mechanisms. The majority of glasses fall into groups that demonstrate extensive recycling of glass. This has important implications for determining provenance using trace elements and isotopes.     

The origins of Byzantine glass from Maroni Petrera,Cyprus

Nineteen glasses from Maroni Petrera, Cyprus, dating to the sixth–seventh centuries ad, have been analysed by energy‐dispersive X‐ray analysis in the scanning electron microscope for major and minor elements. A subset of 15 glasses was also analysed for trace elements, using inductively coupled plasma mass spectrometry. Two groups are identified. The majority is made of glass produced in the coastal region of Syria–Palestine. The smaller group is of high iron, manganese and titanium (HIMT) glass, a widespread type of uncertain origin at the present time. The glasses appear to have undergone relatively minor mixing and recycling, and the glass material is likely to have arrived in Cyprus in the form of raw glass chunks or relatively fresh vessel cullet.     

Mineralogical And Chemical Investigations Of Bloomery Slags From Prehistoric (8th Century Bc To 4th Century Ad) Iron Production Sites In Upper And Lower Lusatia,Germany

More than 400 fayalitic bloomery slags from prehistoric iron production sites in Upper and Lower Lusatia, eastern Germany, as well as bog iron ore samples and intermediary samples of the smelting process, were analysed by chemical and mineralogical techniques. While the precursor bog iron ores exploited in the two regions under investigation were very similar in composition, consisting of low‐manganese/low‐barium as well as high‐manganese/high‐barium types of ore, pronounced differences in slag composition were detected. Slags from 17 investigated sites in Upper Lusatia showed average P₂O₅ contents between 1 and 3 mass%, whereas slags from 15 investigated sites in Lower Lusatia were generally much richer in phosphorus, reaching values as high as 7 mass% P₂O₅. Since a reasonable correlation exists between calcium and phosphorus contents in the slags of the latter sites, it is conjectured that deliberate addition of CaO to the ore/charcoal charge of the bloomery furnace may have taken place in order to fix the phosphorus in the slags effectively. In many samples, this conjecture is being supported by the detection of a slag mineral Ca–Fe phosphate Ca_9?xFe_1+x(PO₄)₇ that presumably crystallized from a residual phosphorus‐rich melt and shows a cotectic relationship to both Ca‐rich fayalite and wustite, as well as to members of the solid solution series magnetite–hercynite.     

Polychromy Analysis on Cypriot Archaic Statues by Non‐ and Micro‐Invasive Analytical Techniques

The polychromy of limestone and terracotta statues from Cyprus attributed to the sixth to fifth centuries bc is analysed using non‐ and micro‐invasive techniques in order to shed light on the use of pigments during the studied period. The strengths and limitations of these methods for the present application are discussed. The identified pigments are iron‐containing compounds (red, yellow, green earths and iron–manganese black). No copper‐containing compounds were detected on the studied objects, despite the wide availability of copper minerals in Cyprus.     

Cargoes of Iron Semi‐Products Recovered from Shipwrecks off the Carmel Coast,Israel

Underwater surveys along the Israeli Carmel coast have revealed six cargoes of iron semi‐products associated with shipwrecks. They are described and dated according to the associated artefacts. Metallographic and chemical analyses on samples from the biggest cargo have determined the stages of the chaîne opératoire, identified the properties of the iron and characterized the iron trade along the Israeli coast. The new discoveries contribute to our understanding of the circulation of iron in the South Levant, which was characterized by an almost complete absence of local iron production. During the Byzantine and Crusader periods, this absence was compensated by long‐distance sea trade, depending on political circumstances and restrictions. Three main types of iron semi‐products were identified: (a) partly consolidated blooms, (b) short pointed bars and (c) elongated pointed bars. The cargoes discovered represent a time period of nearly a millennium. Altogether, 148 iron semi‐products were studied. Of these, 166 were from cargo a, which was dated by coins to around 1130–1200 ce . Those coins could have been imported from Europe for Crusader military and civil uses in the Levant. The iron from cargoes b, d and f, dated perhaps to the Byzantine period, could have been imported from Anatolia or Venice for military and civil purposes.     

Vietnamese (15th Century) Blue‐And‐White,Tam Thai and Lustre Porcelains/Stonewares: Glaze Composition and Decoration Techniques*

EDS, X‐ray fluorescence, Raman spectroscopy, thermal expansion–shrinkage measurement and scanning electron microscopy were applied to determine the elemental components, structural phases and glazing temperatures of the transparent glazes, blue underglaze and overglaze tam thai (including gold‐like lustre) decorations from the 15th‐century Vietnamese porcelains/stonewares found at the Chu Ðâu–My Xa kiln site and in the Cù Lao Chàm (Hôi An) cargo. The ancient technology for colouring the glazes is discussed. The various blue tones in the underglazed décor result from cobalt‐containing manganese ore, with the intentional addition of iron oxide. The overglaze copper‐green and the gold‐like lustre were obtained by dispersing copper in lead‐based glass. The red colour was made using hematite dispersed in lead‐rich flux.     

Fracture‐focused fluid flow in an acid and redox‐influenced system: diagenetic controls on cement mineralogy and geomorphology in the Navajo Sandstone

Differential cement mineralogy is influenced by depositional textures, structural deformation, pore fluid chemistry, and ultimately influences landscape evolution by introducing heterogeneities in erodibility. In Southern Utah, the region West of the Kaibab uplift known as Mollies Nipple (Mollies) in Grand Staircase‐Escalante National Monument exhibits a complex history of fluid–sediment interactions, which has resulted in a localized zone of anomalous diagenetic iron sulfate (jarosite) mineralogy in a well‐exposed dune–interdune deposit within the Navajo Sandstone. Mineralogy and geochemistry of cements within this region are examined using reflectance and imaging spectroscopy, field investigations, microscopy, and whole‐rock geochemical analyses. These data show that the in‐situ jarosite cement is localized to a plane along the highest ridge of the butte, providing an armor along with other secondary cements, which controls the butte's geomorphic evolution. The jarosite cement is associated with other mineralogies suggesting that the sulfate was one of the latest fluid‐related precipitates in the paragenetic sequence. It was preceded by a regional bleaching event, precipitation of clay cements, some localized concretionary iron oxide precipitation, and formation of deformation bands. At least one generation of dense iron oxide mineralization is associated with cataclastic brittle deformation predating the sulfate precipitation. Trace element geochemistry of cements shows certain metal oxide populations associated with extremely high (>2000 ppm) arsenic values. We interpret the combination of spatial mineral distribution, observed paragenetic sequence, and trace element geochemistry to suggest this region experienced acid sulfate diagenesis along fracture‐controlled fluid conduits related to weathering of proximal, unidentified, sulfides, or H₂S associated with deep source beds. Jarosite is highly soluble, and its presence suggests that abundant fluid flow has not occurred in this region since its formation. This terminal cement‐forming event must have occurred prior to sandstone exhumation and erosion to form the current extreme landscape at Mollies. This site exhibits the influence that fluid geochemistry, sedimentary mineralogy, and structural fabric have on geomorphic evolution.     

At the Transition from Late Medieval to Early Modern: the Archaeology of Three Wrecks from Turkey

During surveys in the Rhodian Straits in 2005–06, the staff of the RPM Nautical Foundation discovered three deepwater wrecks which reflect elements of the transition from late medieval to early modern seafaring. The assemblages, and their plotting on site‐plans generated from photographic evidence, point to the finding of a small oared warship equipped with wrought‐iron carriage‐ and swivel‐guns, a small coasting vessel armed with wrought‐iron swivel‐guns, and a larger merchantman equipped with cast‐iron carriage‐guns. While the features of the smaller vessels do not identify their country of origin, those of the larger merchantman have good parallels with known English wrecks. © 2009 The Authors     

TECHNOLOGY OF PRODUCTION OF GHAZNAVID GLAZED POTTERY FROM BUST AND LASHKAR‐I BAZAR (AFGHANISTAN)

Fifteen fragments of glazed pottery were studied by scanning electron microscopy coupled with energy‐dispersive X‐ray analysis (SEM–EDS). The fragments, dated from between the 11th and the 12th centuries, are part of a group excavated at ancient Bust and Lashkar‐i Bazar (southern Afghanistan) and belonging to the International Museum of Ceramics in Faenza. All the samples are characterized by highly calcareous bodies, and all of them but one is coated with a transparent lead glaze; the last fragment is, instead, coated with a turquoise opaque lead–alkali glaze. With three exceptions, the studied fragments show underglaze decorations featuring white, red, green or black motifs applied on to a white, red or black engobe; one of the remaining glazes is applied on to a monochrome white slip and the other two directly on to the ceramic body. Optical microscopy and SEM images show that engobes and decorations were obtained by deposition of differently coloured clayey slips, the composition of which was characterized by EDS analyses. In particular, black engobes and decorative motifs were obtained by recourse to manganese and iron compounds or to chromium, magnesium and iron compounds; it appears that both possibilities could be exploited for obtaining different decorative motifs on the same object.     

Characterization of a Historical Cannonball from the Fortress of San Juan De Ulúa Exposed to a Marine Environment

Metallurgical analyses and chemical characterizations were carried out on historical cannonballs from the Fortress of San Juan de Ulúa, Veracruz, México. Cannonballs dating from the 18th and 19th centuries share metallurgical characteristics similar to those of material coming from a shipment of ammunition found in the wreck of a sunken French ship from the battle of Trafalgar. The analyses show that the base material is grey cast iron with a carbon equivalent of 4.94 and a ferritic–perlitic matrix, in which the high phosphorus content has led to the formation of iron phosphide compounds in conjunction with a homogeneous distribution of carbon graphite flakes of Type C. In addition, corrosion products from samples revealed the presence of various crystalline iron compounds (X‐ray diffraction), mostly highly chlorinated iron compounds identified as akaganeite. X‐ray fluorescence identified various characteristics of the corrosion products as a function of the sampling depth. FT–IR spectroscopy revealed that the main difference between the corrosion products (internal and external) is determined by the number of organic species. Differential scanning calorimetry corroborated that these corrosion products are thermally stable compounds at elevated temperatures.     

Fluid dynamics and fluid‐structural relationships in the Red Lake mine trend,Red Lake greenstone belt,Ontario, Canada

The Red Lake mine trend, a deformation zone in the Archean Red Lake greenstone belt that hosts the world‐class Campbell‐Red Lake gold deposit, is characterized by abundant foliation‐parallel iron‐carbonate ± quartz veins with banded colloform‐crustiform structures and cockade breccias overprinted by silicification and gold mineralization. There is an apparent incompatibility between the cavity‐fill structures of the veins and breccias (typically developed at shallow crustal depths) and the upper greenschist to lower amphibole facies metamorphic conditions recorded in the host rocks (indicating relatively deep environments). This, together with the development of veins along the foliation plane, represents an enigmatic problem that may be related to the interplay between fluid dynamics and stress field. We approach this problem through systematic study of fluid inclusion planes (FIPs) in the vein minerals, including the orientations of the FIPs and the pressure–temperature conditions inferred from fluid inclusion microthermometry. We find that fluid inclusions in the main stage vein minerals (pregold mineralization ankerite and quartz and syn‐ore quartz) are predominantly carbonic without a visible aqueous phase, whereas many inclusions in the postore stage contain an aqueous phase. Most FIPs are subvertical, and many are subparallel to the foliation. High fluid pressure coupled with the high wetting angles of the water‐poor, carbonic fluids may have been responsible for the abundance of brittle deformation features. The development of subvertical FIPs is interpreted to indicate episodic switching of the maximum principal compressive stress (σ₁) from subhorizontal (perpendicular to the foliation) to subvertical (parallel to the foliation) orientation. The subvertical σ₁ is favorable for the formation of foliation‐parallel veins, as fractures are preferentially opened along the foliation in such a stress regime, the origin of which may be linked to the fluid source.     

THE USE OF TRACE ELEMENT ANALYSIS OF ENTRAPPED SLAG INCLUSIONS TO ESTABLISH ORE – BAR IRON LINKS: EXAMPLES FROM TWO GALLO‐ROMAN IRON‐MAKING SITES IN FRANCE (LES MARTYS,MONTAGNE NOIRE,AND LES FERRYS,LOIRET)*

Knowledge of the iron trade in ancient times rests on determining the source of the objects recovered during archaeological excavations. Unfortunately, attributing the origin is not always possible using archaeological tools alone. Trace element data of the ore and the archaeological material (reduction and reheating slags, entrapped slag inclusions from the bloom, bar iron and iron blades) from two Gallo‐Roman iron‐making centres, Les Martys (Montagne Noire) and Les Ferrys (Loiret), were determined using ICP–AES/MS and LA–ICP–MS. The results highlight a continuity of composition that makes it possible to establish a link between the initial ore and the semi‐finished iron products.     

Iron mineralization and dolomitization in the Paran Fault zone,Israel: implications for low‐temperature basinal fluid processes near the Dead Sea Transform

Petrography, Eh‐pH calculations and the stable isotope composition of oxygen are used to interpret geochemical processes that occurred during iron oxide mineralization and dolomitization along the Menuha Ridge segment of the Paran Fault, southern Israel, adjacent to the Dead Sea Transform (DST). Iron mineralization is strongly localized in the fault zone as ferruginous lenses, whereas Fe dolomitization spreads laterally into the Cenomanian‐Turonian carbonate host rock as stratabound beds. The average oxygen isotope fractionation between syngenetic quartz and iron oxides in the ferruginous lenses gives a temperature of 50 ± 10°C and δ¹⁸O SMOW water = ?3.5‰; consistent with an origin from metalliferous groundwater flow in the sedimentary basin. Ferroan dolomite initially formed under strongly reducing conditions, but this was followed by oxidation and pseudomorphic replacement of the dolomite by a mesh of fine‐grained iron oxides (simple zoned dolomites). This cycle of ferroan dolomite formation and replacement by iron oxides was repeated in complex zoned dolomites. Dolomite oxygen isotope compositions fall into two groups: a high δ¹⁸O group corresponding to the simple zoned dolomites and non‐ferroan dolomites and a low δ¹⁸O group corresponding to the complex zoned dolomites. Water‐rock calculations suggest that the epignetic dolomites formed under fluid‐buffered conditions: the high δ¹⁸O group are indicated to have formed at temperatures of ca. 25°C for waters with δ¹⁸O = ?4 to 0‰; the low δ¹⁸O complex zoned dolomites at 50–75°C for waters with the same isotopic composition. A kinetic calculation for a complex zoned dolomite‐bearing bed indicates that dolomitization must have occurred at high values of the dolomite saturation index. This requirement for high Mg supersaturation and the indication that epigenetic dolomitization is more protracted in stratigraphically deeper formations located closer to the DST is consistent with models proposing that Mg‐rich solutions originated in the Dead Sea Rift.     

ANTIMONATE OPAQUE GLAZE COLOURS FROM THE FAIENCE MANUFACTURE OF LE BOIS D’ÉPENSE (19TH CENTURY,NORTHEASTERN FRANCE)*

Three types of antimony‐based, opaque ceramic colours were used in the faience workshop of Le Bois d’Épense during the first decades of the 19th century; that is, yellow, tawny and green. Yellow is generated by lead antimonate crystals (Naples Yellow), which are incorporated into an uncoloured glass matrix. According to SEM–EDS measurements, these pigments contain iron. The tawny colour is the optical result of the combined presence of similar yellow, iron‐bearing lead antimonate particles in a Fe‐rich, brownish glass matrix. The green opaque colour is produced by the combination of a blue cobalt glass and yellow Pb–Sn–Fe‐antimonate crystals. Cores of zoned pigments lighten the recipes, according to which the pigments were produced. First, they were synthesized by calcination, ground and then mixed with a colourless, brown or blue glass powder. The resulting powder mixture was added to a liquid agent and used as high‐temperature ceramic colour.     

Ancient Mining and Smelting Activities in the Wadi Abu Gerida Area,Central Eastern Desert,Egypt: Preliminary Results

Old mining and smelting features in the Abu Gerida area have been studied using field observations, microscopy and SEM–EDS to detect the ores that were exploited in antiquity. There are two groups of shafts in the area. The first group encloses secondary copper minerals and is associated with glassy slags containing copper prills. The other group is associated with hematite that was extracted and transferred to a smelting station to the west of the mining site, where iron slags and charcoal fragments are found. These slags are composed mainly of wüstite, fayalite–kirschsteinite and traces of metallic iron. Pottery fragments from this area were dated to the Ptolemaic Period, which may be the age of iron exploitation. Copper might have been exploited earlier.     

ANALYSIS OF FIRST MILLENNIUM bc GLASS VESSELS AND BEADS FROM THE PICHVNARI NECROPOLIS,GEORGIA*

The Pichvnari necropolis on the Black Sea coast of Georgia lies in an area known in the late first millennium as ‘Colchis’, on part of the trade route leading to the Orient. The burials of the necropolis date to the late fifth century bc and frequently contain grave goods, including extremely well‐preserved polychrome glass beads and core‐formed vessels. This paper presents a study of these vessels both stylistically and archaeologically and using SEM–WDS and LA–ICPMS. It reveals that the vessels have compositional differences that may point to multiple manufacturing sites. One of the vessels appears stylistically unique and may exhibit one of the earliest uses of manganese as a decolorizer. Major and minor element data for the vessels suggest that they may belong to the same ‘Levantine’ group as many Roman glass objects, suggesting that a source of sand on the coast of the Levant could have been used in their production. The beads clearly show glass with both natron‐ and plant ash‐based flux with distinct rare earth compositions, showing multiple sites of production, some of which were probably either in the Middle East or the Indian subcontinent.     

AN ANALYSIS OF THE GEM‐BLUE GLAZE OF YE WANG'S KOJI POTTERY*

Koji pottery is a glazed ceramic art used widely for figurines. In early Taiwan, it was employed in temple construction for decorative purposes. Ye Wang (1826–87) is the first historically documented Koji artist of Taiwan and also the most prominent Koji pottery artist, noted for his modelling and glazing skills. Unfortunately, his unique technique was lost following his death in 1887. In order to provide vital information for ongoing conservation work on Koji pottery, this study analysed the physical and chemical characteristics of Ye Wang's gem‐blue glaze, to discover the glaze formula. DSC combined with the two‐thirds rule revealed that the firing temperature of Ye Wang's works of art was most probably around 878–923°C. EPMA revealed that the gem‐blue glaze has high alkali levels, and belongs to the PbO–K₂O–B₂O₃–Na₂O–SiO₂ system, deriving its unique colour from copper, iron, manganese and cobalt. This study found high potassium levels in the gem‐blue glaze, which are generally a characteristic of traditional Chinese glazes. In addition, a unique discovery of boron, commonly used in famille rose, was also identified in the glaze. By comparing spectra of historical and reconstructed glazes and adjusting the proportion of chromophoric elements, this study found a glazing formula with colours close to those of Ye Wang's gem‐blue glaze.     

Granite‐related overpressure and volatile release in the mid crust: fluidized breccias from the Cloncurry District,Australia

The source and transport regions of fluidized (transported) breccias outcrop in the Cloncurry Fe‐oxide–Cu–Au district. Discordant dykes and pipes with rounded clasts of metasedimentary calc–silicate rocks and minor felsic and mafic intrusions extend several kilometres upwards and outwards from the contact aureole of the 1530 Ma Williams Batholith into overlying schists and amphibolites. We used analytical equations for particle transport to estimate clast velocities (≥20 m sec^?1), approaching volcanic ejecta rates. An abrupt release of overpressured magmatic‐hydrothermal fluid is suggested by the localization of the base of the breccias in intensely veined contact aureoles (at around 10 km, constrained by mineral equilibria), incorporation of juvenile magmatic clasts, the scale and discordancy of the bodies, and the wide range of pressure variation (up to 150 MPa) inferred from CO₂ fluid inclusion densities and related decrepitation textures. The abundance of clasts derived from depth, rather than from the adjacent wallrocks, suggests that the pressure in the pipes was sufficient to restrict the inwards spalling of fragments from breccia walls; that is, the breccias were explosive rather than implosive, and some may have vented to the surface. At these depths, such extreme behaviour may have been achieved by release of dissolved fluids from crystallizing magma, in combination with a strongly fractured and fluid‐laden carapace, sitting under a strong, low permeability barrier. The relationship of these breccias to the Ernest Henry iron‐oxide–Cu–Au deposit suggests they may have been sources of fluids or mechanical energy for ore genesis, or alternately provided permeable pathways for later ore fluids.     

Electron paramagnetic resonance of mosaic glasses from the Mediterranean area*

Ancient mosaic glass tesserae sampled from archaeological sites located in the Mediterranean area have been analysed by Inductively Coupled Plasma‐Optical Emission Spectroscopy (ICP‐OES). The aim of the research was to understand the role played by 3d transition metals in the optical properties of such samples. In order to better identify the specific effect of the main chromophorous element, modern samples have been prepared in the laboratory by adding to a colourless base frit controlled concentrations of colouring oxides. Samples with compositional and optical properties similar to the ancient ones have been obtained. For all these modern samples, as well as for all the ancient ones, electron paramagnetic resonance (EPR) measurements have been performed. The features of the EPR spectra could be successfully associated with the presence and abundance of the paramagnetic colouring ions (namely iron, manganese and copper) and to their oxidation states. This could be a basic step towards understanding the provenance and chronological attribution of mosaic glass tesserae.     

MANGANESE STAINING OF ARCHAEOLOGICAL GLASS: THE CHARACTERIZATION OF Mn‐RICH INCLUSIONS IN LEACHED LAYERS AND A HYPOTHESIS OF ITS FORMATION

During the study of a large number of archaeological glass fragments, manganese‐rich inclusions in leached layers were observed in a limited number of cases. This phenomenon occurs only in black‐coloured leached layers. Since the formation mechanism of such manganese‐rich inclusions is still unclear, a combination of several analytical techniques was used in order to investigate this phenomenon and, more specifically, to obtain more information on (a) the composition and morphology of the inclusions, (b) the chemical state of Mn and (c) the 3D morphology of the inclusions. A mechanism that might explain the formation of these inclusions is proposed.