THE DETERMINATION OF BRICK PROVENANCE AND TECHNOLOGY USING ANALYTICAL TECHNIQUES FROM THE PHYSICAL SCIENCES*†

This work applies established analytical techniques from the physical sciences to Irish brick, in order to gather evidence of ceramic technologies, provenance and sources of raw materials. Petrographic microscopy, X‐ray diffractometry and scanning electron microscopy with an energy‐dispersive X‐ray diffraction attachment were used to study the brick of Rathfarham Castle, Dublin, built c. 1618, where clay brick was introduced in 1771. Local clay was fired in the laboratory and analysed in a similar manner. The petrography of the pointing mortar was studied in order to gather evidence of ceramic provenance. This paper concludes that the brick was hand‐ moulded with a silica‐based, predominantly non‐calcareous clay of glacial origin, gathered locally, including fluxes and a high percentage of non‐plastic material. The mineralogy and petrography of the brick, together with the presence of pebbles and a coarse matrix, suggest that the raw clay was probably gathered from a glacial deposit. The presence of abundant pebbles and colour inhomogeneities suggests a lack of processing of the raw clay. The brick was probably fired in clamps at top firing temperatures ranging from 750°C to above 900°C. Transformation of limestone temper involving the breakdown of calcite and the generation of calcium silicates, and the new formation of plagioclase, high‐temperature quartz, hematite and spinel were revealed. The presence of spinel in ‘hot spots’ indicates that fuel was added to the raw clay in order to assist firing.     

ARCHAEOMETRIC INVESTIGATIONS OF SGRAFFITO CERAMIC TILES (FIFTEENTH‐SIXTEENTH CENTURIES) RECOVERED FROM EXCAVATIONS IN UDINE (NORTH‐EAST ITALY)*

Most of the Renaissance sgraffito tiles excavated in Udine (Italy) constitute a homogeous group, the tile body having a CaO/MgO molar ratio ?= 3:2. They were produced using a dolomite‐ and calcite‐containing clay fired at 900–950°C. A small group of samples, with a lower firing temperature and a CaO/MgO ratio ?= 2:3, was probably produced in a different factory. Slip and transparent glaze, characterized by optical microscopy and inductively coupled plasma atomic emission spectrometry, are an illite‐rich clay and a lead silicate, respectively.     

PAUL‐LOUIS CYFFLÉ'S (1724–1806) TERRE DE LORRAINE: A TECHNOLOGICAL STUDY

Fragments of four Terre de Lorraine biscuit figurines were subjected to porosity analysis, X‐ray fluorescence analysis, X‐ray diffraction analysis, backscattered‐electron image analysis—coupled with energy dispersive spectrometry—and electron backscatter diffraction analysis to determine the porosity, bulk, major, minor and trace element compositions, and the composition and the proportion of their constituent phases. Cyfflé's Terre de Lorraine wares embrace two distinct types of paste, a calcareous and an aluminous–siliceous one. Both are porous (9–25% water adsorption). The former consists of a mixture of different proportions of ground quartz or calcined flint, ground Pb‐bearing glass and calcium carbonate with a refractory clay. The firing temperature was between 950 and 1050°C. For the latter, Cyfflé mixed ground pure amorphous SiO₂, ground quartz or calcined flint, ground porcelain, ground Na–Ca‐glass and coarse‐grained kaolinite with a fine‐grained kaolinitic clay. The figurines were fired below 1000°C. The result was a porous, hard paste porcelain‐like material. Cyfflé's recipes for both pastes can be calculated from the chemical and the modal analyses.     

Archaeometric study of medieval pottery excavated at Stari (Old) Ras,Serbia

A combined study of a series of polychromatic and monochromatic glazed medieval pottery shards excavated from the archaeological area of Stari (Old) Ras in southern Serbia, including petrographic and chemical analysis, powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy, allowed us to clearly distinguish between two groups of ceramics. Ras pottery, made of fine-grained well-cleaned clay and characterised by a rich mineral assemblage, was produced by firing in a temperature range between 800 and 900 °C. Reljina Gradina ceramics were produced at similar temperatures from materials which, with regard to mineralogical and chemical composition, show clear similarity with local clay, suggesting that these samples are of local origin and production. This work is the first systematic archaeometric study of medieval pottery excavated on the territory of Serbia.     

The Mineralogical Characteristics of the Lamboglia 2 Roman‐Age Amphorae from the Central Adriatic (Croatia)*

The mineralogical characteristics of four Lamboglia 2 Roman‐age amphorae excavated from ancient underwater shipwreck localities in the central Adriatic were investigated. X‐ray diffraction and optical microscopy analyses showed that the amphorae have similar primary mineral compositions, mainly consisting of quartz, plagioclase, potassium feldspar, diopside, illite and calcite, most probably originating from clayey Eocene flysch deposits used as raw materials in manufacture. The difference in mineral composition between these samples is recognized from the presence or absence of melilite, high‐magnesium calcite, aragonite, gypsum and analcime. It was shown that melilite is a secondary mineral formed during the firing process, while the others, which build up through incrustation of marine benthonic communities on the amphora walls and fill the cracks in the amphora bodies, were formed by crystallization in seawater. The firing of the original pieces of amphorae showed that melilite could be formed at temperatures higher than 800°C, most probably through interaction between calcite and silicate minerals present in the raw materials. The presence of melilite, and the absence of illite and calcite, were used to estimate the firing temperature of the amphorae during their production.     

Red calcite: an indicator of paleo‐karst systems associated with bauxitic unconformities

A unique red calcite generation, which fills fractures/cavities, is hosted by Mesozoic carbonates in the Transdanubian Range, Hungary. Solid inclusions are located along growth zones of calcite. Hematite, the most abundant solid inclusion, gives the red colour of it. Outcrop‐scale geometry, mineralogical features and detrital mineral assemblage (hematite, gibbsite, goethite, kaolinite, smectite, illite, Cr‐spinel, monazite, xenotime, zircon, apatite and Ti‐oxide) of calcite precipitates suggest strong correlation between the calcite and nearby karst bauxite deposits. Fluid inclusion petrography and microthermometry (T < 50°C; salinity from 0 to 0.17 NaCl eq. w%) of primary fluid inclusions, and the stable isotope trend of the calcite, following the meteoric water line, clearly indicate vadose and phreatic meteoric origin in a near‐surface karst system. The late Cretaceous to mid‐Eocene unconformity‐related cavity‐filling deposits occur close to the surface; indicating that the most recent Quaternary exhumation re‐exposed those surfaces that existed at the time of calcite mineralization. Thus, red calcite precipitates are interpreted as being speleothems, vestiges of the subterranean part of the pre‐Middle Eocene karst. The infiltrated, fine bauxite particles enclosed by the calcite are the witnesses of the once areally extensive pre‐Middle Eocene bauxitic blanket that became partially eroded by the time of the deposition of the cover beds. Red calcite when found in core samples may provide good evidence on bauxite formation associated with the overlying unconformity, even if it was later removed by erosion. Therefore, presence or absence of red calcite may be used as distinguishing criteria between karst episodes with or without bauxite formation.     

A STUDY ON LATE MEDIEVAL TRANSPARENT‐GLAZED POTTERY AND ARCHAIC MAJOLICA FROM ORVIETO (CENTRAL ITALY)*

Nineteen samples of medieval transparent‐glazed pottery and archaic majolica from Orvieto (central Italy) were studied. They were classified by archaeological criterion as follows: five transparent‐glazed fragments with green and brown decorations (first half of the 13th century), eight green transparent‐glazed fragments (13th century) and six tin‐glazed fragments with green and brown decorations (second half of the 13th century). SEM–EDX, XRD (the Rietveld method) and XRF were used to characterize the chemical and mineralogical compositions both of the bodies and the coatings. In all of the samples, the paste is Ca‐rich with CaO contents as high as 13–20 wt%. The mineralogical composition is compatible with a firing temperature of about 950°C, which is the typical temperature reached in a wood kiln. No difference was observed between the bodies of transparent‐ and tin‐glazed pottery. In the case of transparent glazes, the burial conditions lead to heavy weathering of the samples. However, on the basis of the analyses carried out in non‐weathered areas, the typical composition is PbO 55–65 wt%, SiO₂31–35 wt%. In tin glazes, the tin is scattered on the mass of the glaze as SnO₂crystals with a concentration of 7–14 wt%. Concerning the decorations, it is established that the green colour is due to the presence of copper, while manganese is responsible for the brown colour. These pigments, which represent the typical colours of ‘archaic majolica’, are spread through the glaze homogeneously, apart from one case in which there is clear evidence of manganese oxide crystals.     

Minero-petrographic characterization of fine ware from Cales (South Italy)

79 samples of black glazed pottery, Terra sigillata, fine common ware, and production indicators were recovered in the archaeological site of Cales and investigated via a multi-analytical program (polarized light microscopy, thermal analyses, XRPD, XRF, FESEM, FESEM-EDS). Among the materials, finds of important production indicators, represented by welded pieces of black glazed pottery and spacers, attest a local production. Polarized light microscopy shows that the inclusions consist of feldspar, quartz, mica, calcite, and lithic fragments of both volcanic and sedimentary nature. Additional information about the mineralogical assemblage comes from the XRPD that revealed the presence of neoformed Ca-silicates, indicating equivalent firing temperatures ranging from 750 to 1050°C. All the samples show a Ca-rich character and an extreme compositional homogeneity, including the production indicators. The comparison with some Ca-rich Campanian clay raw materials shows a greater affinity with the Mio-Pliocene marine clay sediments of the Apennine sector, which include local clays. This allowed us to formulate the first hypotheses about clay sources used to produce fine pottery during the third century BCE to the early imperial period in Cales.     

MINERALOGY OF MEDIEVAL SLAGS FROM LEAD AND SILVER SMELTING (BOHUTÍN,PŘÍBRAM DISTRICT,CZECH REPUBLIC): TOWARDS ESTIMATION OF HISTORICAL SMELTING CONDITIONS*

Slags from the Pb/Ag medieval (14th century) smelting plant located at Bohutín, P?íbram district, Czech Republic, were studied from the mineralogical and geochemical points of view. Two types of slags were distinguished: (i) quenched slags formed mainly by Pb‐rich glass and unmelted residual grains of SiO₂ and feldspars, and (ii) crystallized slags mainly composed of Fe‐rich olivine (fayalite) and glass. The mean log viscosity value of the slags calculated for 1200°C was 2.119 Pa s. The morphology of olivine crystals was used to estimate the cooling rates of the melt, for some slags indicating rates > 1450°C/h. The projection of the bulk composition of slags onto the SiO₂–PbO–FeO ternary system was used for rough temperature estimates of slag formation, lying probably between 800 and 1200°C.     

A Case of Ancient Bladder Stones from Oluz Höyük,Amasya, Turkey

A biological object was recovered from the pelvic region of an adult woman coded to SK13 unearthed from Oluz Höyük in Amasya, Turkey. The skeleton was dated to the medieval period on the basis of the burial customs and the calibrated ¹⁴C dates. The find was identified as a bladder stone on morphological, radiographic and chemo‐analytical grounds with the help of X‐ray diffraction, polarised energy dispersive X‐ray fluorescence spectroscopy, confocal Raman spectroscopy, and microscopic techniques. The mineralogical composition of urinary stone was found to be as calcium phosphate (apatite). Bladder stone disease is endemic in poor agricultural regions where the typical diet is mostly based on grain carbohydrate consumption with scarce intake of animal protein. Copyright © 2013 John Wiley & Sons, Ltd.     

Lipid Residues from Low‐Fired Pottery

This paper assesses the fate of lipids associated with low‐temperature and pit‐fired pottery to determine to what degree organic compounds persist or are removed during short‐firing episodes below 800 °C. Three different types of clay were fired using contrasting techniques including at 400 °C for 4 h in a muffle furnace, and pit‐firing in which pottery was fired to higher temperatures but for shorter periods of time. Total lipid extracts obtained by solvent extraction of test sherds were screened using gas chromatography‐flame ionization detection (GC‐FID) to determine the lipid concentrations and gas chromatography–mass spectrometry (GC–MS) to identify the organic compounds present. The results showed that firing of clay removes all naturally occurring alkyl lipids; however, during pit‐firing, diterpenoid lipids were introduced into the clay as a condensate from pine ( Pinus spp.) wood used as fuel. These results confirm that alkyl lipids, e.g., fatty acids, can be reliably associated with the use of vessels, although caution is required when interpreting the origins of lipids that might derive from fuel used in firing.     

Organic–inorganic rock–fluid interactions in stylolitic micro‐environments of carbonate rocks: a FIB‐TEM study combined with a hydrogeochemical modelling approach

Stylolites and the interfaces to the host limestone have been investigated by means of a multidisciplinary analytical approach (thin section microscopy, FIB‐TEM, organic geochemistry and petrography). Carbonate dissolution assuming different boundary conditions was simulated by applying a generic hydrogeochemical modelling approach. It is the conceptual approach to characterize and quantify traceable organic–inorganic interactions in stylolites dependent on organic matter type and its thermal maturity, and to follow stylolite formation in carbonates as result of organic matter reactivity rather than pressure solution as a main control. The investigated stylolite samples are of Upper Permian (Lopingian, Zechstein), Middle Triassic (Muschelkalk) and Late Cretaceous (Maastrichtian) age and always contain marine organic matter. The thermal maturity of the organic matter ranges from the pre‐oil generation zone (0.4–0.5% R_r) to the stage of dry gas generation (>1.3% R_r). The results of the generic hydrogeochemical modelling indicate a sharp increase of calcite dissolution and the beginning of stylolite formation at approximately 40°C, which is equivalent to a depth of less than 800 m under hydrostatic conditions considering a geothermal gradient of 30°C and a surface mean temperature of 20°C. This temperature corresponds to the pre‐oil window when kerogens release an aqueous fluid enriched in carbon dioxide and organic acids. This aqueous fluid may change the existing pore water pH or alkalinity and causes dissolution of carbonate, feldspar and quartz, and clay mineral precipitation along the stylolite. Dissolution of limestone and dolostone leads to reprecipitation of calcite or dolomite opposite of the dissolution side, which indicates only localized mass redistribution. All these integrated hydrogeochemical processes are coupled to the generation of water during organic matter maturation. In all of the calculated hydrogeochemical scenarios, H₂O is a reaction product and its formation supports the suggested hypothesis.     

CHEMICAL–MINERALOGICAL ANALYSES AND MICROSTRUCTURAL STUDIES OF PREHISTORIC POTTERY FROM RAHMATABAD,SOUTH‐WEST IRAN*

A series of prehistoric pottery samples excavated from Rahmatabad, south‐west Iran, were investigated using XRF and XRD analyses to determine their chemical and mineralogical compositions. The sample microstructures were also studied by SEM/EDX. The relative similarity of compositions, the fine, dense and homogeneous microstructures and the presence of high‐temperature phases such as diopside and mullite showed the use of high firing temperatures, in the range 950–1050°C. This, along with the homogeneity in shape, decoration and size ranges of the ware, all indicate the adoption of specialized pottery‐making techniques by the potters of Rahmatabad in the fifth to fourth millennia bc .     

TIME‐OF‐FLIGHT NEUTRON DIFFRACTION CHARACTERIZATION OF CERAMIC FINDINGS FROM SOUTHERN AND WESTERN SICILY*

We present the results of a study that is part of a wider research programme regarding knowledge of the initial living phases of Sicilian agricultural and pastoral society. Three sets of ceramic samples were analysed through time‐of‐flight neutron diffraction (TOF‐ND) to derive information about the composition of the clay and the manufacturing techniques. The first two sets of sherds came from an excavation in Licata, close to Agrigento, and are composed of findings dated around the third century bc , while the third set was of samples from prehistoric sites located in the northwestern part of Sicily. Measurements were performed to obtain a quantitative identification of the mineralogical composition of the samples in a totally non‐destructive way. Hints about manufacturing techniques and firing temperatures are derived to provide information on provenance and production processes of the objects.     

Ancient Egyptian Pottery from the Subsurface Floodplain of the Saqqara–Memphis Area: Its Mineralogical and Geochemical Implications*

Potsherds recovered from the Saqqara–Memphis floodplain in Egypt, dated according to their typology and radiocarbon dating of the included sediments, are analysed geochemically and mineralogically to identify source materials and fabrication characteristics. Pottery layers were identified and potsherds were recovered from several settlement levels. Sherd typology was used to identify sherds from four periods (the Old and New Kingdoms, and from the Late Period to the Ptolemaic). The Pharaonic pieces were found at depths of between 8 and 12 m and the later material was between 6 and 3 m. Chemical analyses of the potsherds revealed three main source materials: local Nile silt, marl clay and mixed Nile silt–marl. Two marl clay types were recognized: marl clay from Upper Cretaceous marine sediment and another one from Late Pliocene deltaic sediments. The mineralogical composition of the pottery samples shows that the estimated firing temperature was about 850–900°C. No consistent differences in sherd mineralogy and geochemistry were found according to pottery types, so that the ancient Egyptian potters used essentially the same materials throughout the Pharaonic period. However, this initial study has revealed the existence of extensive pottery‐rich occupation sites buried within the Nile floodplain deposits between Memphis and Saqqara.     

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

Studying the process of enamel powder preparation for émail champlevé by colour measurements and μ‐X‐ray mappings

Colour measurements and non‐destructive μ‐X‐ray mappings have been used for the first time in a comprehensive study of medieval émail champlevé works from different production areas in France and Germany. This approach has given a new insight into the enamel powder preparation process of the glass material used for enamelling. Colour measurements demonstrated that all production centres used glass of very similar hues, but with large differences in colour saturation. The μ‐X‐ray mapping results of blue enamels are described by a semi‐qualitative approach. Significant variations in oxide contents of lead, cobalt, manganese and antimony oxides were found. The variations suggest that more than one glass material was used to prepare the powder for enamelling. The variations in antimony and cobalt show that glass had different degrees of opacity and colour depth. The manganese and lead contents, which do not correlate with the cobalt or antimony contents, indicate that probably glass of different base compositions was used to prepare the enamel powder for one champlevé field.     

A SCIENTIFIC INVESTIGATION ON THE PROVENANCE AND TECHNOLOGY OF A BLACK‐FIGURE AMPHORA ATTRIBUTED TO THE PRIAM GROUP*

The restoration of a Greek black‐figure amphora provided an opportunity to study the provenance and production technology of the vase. The composition of the ceramic body, determined by inductively coupled plasma optical emission spectroscopy (ICP–OES), matches that of Attic products. Investigation by X‐ray diffraction and reflectance spectroscopy suggests a maximum firing temperature around 900°C and a body re‐oxidation temperature around 800°C, respectively. The morphology and composition of black, red and dark red surface areas were studied by scanning electron microscopy and X‐ray energy‐dispersive analysis; the black areas show the features of a typical well‐vitrified black gloss, while the red areas were most probably obtained by simple burnishing of the body; the dark red additions, on the other hand, are the likely result of a partial re‐oxidation of a clay–ochre mixture.     

ACCESSORY MINERALS AS TRACERS IN THE PROVENANCING OF ARCHAEOLOGICAL MARBLES,USED IN COMBINATION WITH ISOTOPIC AND PETROGRAPHIC DATA*

Thirty‐eight archaeological marbles (Roman and medieval) from Modena and Reggio Emilia (northern Italy) were provenanced using the accessory minerals as tracers and the results were compared with those inferred for the same artefacts using isotope composition and MGS (maximum grain size of calcite grains). The number of inferred possible sources is generally lower when using the mineralogical method, which therefore seems to be suited to marble provenancing.