Potassium–Calcium Glass: New Data and Experiments*

The chemical composition of potassium–calcium ‘wood‐ash’ glass reflects the elemental pattern of the involved non‐volatile base materials in quartz sand, wood ash and possibly potash. The essential elemental ratio K₂O/CaO of wood ash varies between 0.2 and 0.8, and depends on the habitat and geological substratum of the wood rather than on the tree species; ratios between 1.0 and 3.0 in wood‐ash glass are only possible when potash is added as a third base material. Melting temperatures of wood‐ash glass sensu stricto, termed K–Ca‐2, produced with the two raw materials quartz sand and wood ash, are between 1250°C and 1400°C, while those of three‐component‐glasses, termed K–Ca‐3, are between 900°C and 1250°C, according to the amount of added potash. Experimentally produced glass displays different hues, from colourless to brown, olive‐green and pink, according to the chemical composition of the wood ash. Elevated MnO concentrations between 0.5 and 3 wt% may originate from wood ash and are hence not necessarily an indicator of colour‐inhibiting additives. Phosphate stemming from wood ash is an essential discriminator between wood‐ash glass and potash–lime glass. Because wood ash contains only minor amounts of sodium, wood‐ash glass with equal concentrations of potassium and sodium is a hybrid glass type, where besides quartz sand, wood ash, possibly potash and also soda‐rich cullet have been applied for glass production.     

Isothermal Time‐Series Determination of the Rate of Diffusion of Water in Pachuca Obsidian*

Friedman and Smith's (1960) article introducing an exciting, potentially precise and inexpensive method of dating obsidian artefacts has thus far failed to reach its potential. Numerous efforts to refine, improve and even redevelop the method since that time have similarly failed to achieve the original promise. Only within the last eight years have significant improvements been made, due to both improved analytical techniques and a better understanding of the hydration process. However, most of our mechanistic understanding of the interaction of water with rhyolitic glass is based on experiments performed on melts and glasses at temperatures above their glass transitions, conditions inappropriate for investigation of near‐surface environmental conditions. Unfortunately, studies detailing the temporal evolution of the diffusion profile at low temperatures are rare, and few useful data are available on the low‐temperature diffusive hydration of silicate glasses. This paper presents data on the experimental hydration of obsidian from the Pachuca source (a.k.a. Sierra de las Navajas, Basin of Mexico) at 75°C for times ranging from 3 to 562 days, and compares these results with data for samples obtained from a stratigraphic excavation of the Chalco site in the Basin of Mexico. Samples have been analysed using secondary ion mass spectrometry (SIMS) to provide concentration/depth data. While 75°C is still significantly above the temperatures at which archaeological obsidians hydrate, it is well below the glass transition temperature (approx. 400°C) and thus processes are likely to be similar to those that occur in nature, but fast enough to be observed over a laboratory timescale. The results demonstrate that a simple square‐root‐of‐time model of the evolution of the diffusion profile is not adequate to describe the diffusion process, as measured diffusion profiles exhibit the effects of concentration‐ and time‐dependent, non‐Fickian diffusion. With progressive hydration, characteristic diffusion coefficients first decrease, then increase with time. Surface concentration increases with time, but an intermediate plateau is observed in its time evolution that is consistent with results obtained from the suite of Chalco samples. Both of these effects have been observed during diffusion in glassy polymer systems and are associated with the build‐up and relaxation of self‐stress caused by the influx of diffusing material.     

ROMAN GLASS‐MAKING AT COPPERGATE,YORK? ANALYTICAL EVIDENCE FOR THE NATURE OF PRODUCTION*

Ceramic vessels and associated vitreous debris, excavated at Coppergate, York, UK, have been interpreted as the remains of Roman glass‐making from the raw materials. This paper reports the results of analysis of this assemblage by XRF, ICPS, XRD, SEM– EDAX and thin‐section petrography. These findings suggest that some ceramic vessels, used as crucibles, have been subjected to temperatures up to 1200°C, well above the firing temperatures of the local domestic assemblage from which they were selected. Analysis of quartz‐rich debris, intimately mixed with glass in some samples and in others interleaved with glassy phases, indicates partially reacted glass‐making raw materials, with α‐quartz, tridymite and cristoballite phases represented. This could represent evidence either of a failed attempt to frit the raw materials, or a batch that had not fully fused. Variability in the composition of glass at the site is viewed in the light of glass‐making technology, and possible interpretations concerning this episode are discussed in the light of the archaeological evidence.     

Quantitative analysis of COH fluids synthesized at HP–HT conditions: an optimized methodology to measure volatiles in experimental capsules

The quantitative assessment of COH fluids is crucial in modeling geological processes. The composition of fluids, and in particular their H₂O/CO₂ ratio, can influence the melting temperatures, the location of hydration or carbonation reactions, and the solute transport capability in several rock systems. In the scientific literature, COH fluids speciation has been generally assumed on the basis of thermodynamic calculations using equations of state of simple H₂O–nonpolar gas systems (e.g., H₂O–CO₂–CH₄). Only few authors dealt with the experimental determination of high‐pressure COH fluid species at different conditions, using diverse experimental and analytical approaches (e.g., piston cylinder + capsule piercing + gas chromatography/mass spectrometry; cold seal + silica glass capsules + Raman). In this contribution, we present a new methodology for the synthesis and the analysis of COH fluids in experimental capsules, which allows the quantitative determination of volatiles in the fluid by means of a capsule‐piercing device connected to a quadrupole mass spectrometer. COH fluids are synthesized starting from oxalic acid dihydrate at P = amb and T = 250°C in single capsules heated in a furnace, and at P = 1 GPa and T = 800°C using a piston‐cylinder apparatus and the double‐capsule technique to control the redox conditions employing the rhenium–rhenium oxide oxygen buffer. A quantitative analysis of H₂O, CO₂, CH₄, CO, H₂, O₂, and N₂ along with associated statistical errors is obtained by linear regression of the m/z data of the sample and of standard gas mixtures of known composition. The estimated uncertainties are typically <1% for H₂O and CO₂, and <5% for CO. Our results suggest that the COH fluid speciation is preserved during and after quench, as the experimental data closely mimic the thermodynamic model both in terms of bulk composition and fluid speciation.     

THE ANCIENT MINE OF SERVETTE (SAINT‐MARCEL,VAL D’AOSTA,WESTERN ITALIAN ALPS): A MINERALOGICAL,METALLURGICAL AND CHARCOAL ANALYSIS OF FURNACE SLAGS*

The Cu–Fe mining district of Servette is located in the valley of Saint‐Marcel (Val d’Aosta) at about 1800 m a.s.l. in the western Italian Alps. A large furnace slag deposit occurs near the Servette mine. Slags are mainly constituted by silicate and oxide in a glassy matrix, with disseminated sulphides and iron–copper alloys, and they record temperatures of 1380–1100°C. Radiocarbon dating of slag charcoals has shown that metallurgy in this site took place around ad 890–980. The charcoal analysis has shown that coniferous wood was mainly utilized, and intensive exploitation over the centuries led to a change in the composition of the local woods.     

THE APPLICATION OF A PORTABLE X‐RAY FLUORESCENCE SPECTROMETER TO THE ON‐SITE ANALYSIS OF GLASS VESSEL FRAGMENTS FROM SOUTHERN THAILAND*

Ancient glass vessel fragments belonging to the seventh to ninth centuries ad , from the Ko Kho Khao, Laem Pho and Khuan Lukpad sites in southern Thailand, were studied. The glass vessel fragment samples are a collection belonging to the Department of Archaeology, the 15th Regional Office of Fine Arts of Thailand. The chemical compositions of the glasses were analysed using a modified portable energy‐dispersive X‐ray fluorescence spectrometer (OURSTEX 100FA‐II) by the introduction of a MOXTEK^® AP3.3 polymer window (5 mm²?) to the KETEK silicon drift detector for the measurement of light elements. The non‐destructive analysis was performed at the National Museum, Phuket, in Thailand. It is shown that the glass chemical compositions belong to mineral and plant‐ash based soda–lime–silicate glass. The origins of the glass artefacts are discussed in terms of raw materials and glass decoration, and compared with previously reported similar typological glasses from sites in the port city of Rāya and the Monastery of Wadi al‐Tur in Egypt.     

Radical changes in Islamic glass technology: evidence for conservatism and experimentation with new glass recipes from early and middle Islamic Raqqa,Syria*

The chemical analysis of excavated glass fragments from dated archaeological contexts in Raqqa, Syria, has provided a detailed picture of the chemical compositions of artefacts deriving from eighth to ninth and 11th century glassmaking and glassworking activities. Evidence for primary glass production has been found at three excavated sites, of eighth to ninth, 11th and 12th century dates; the first two are discussed here. The 2 km long industrial complex at al‐Raqqa was associated with an urban landscape consisting of two Islamic cities (al‐Raqqa and al‐Rafika) and a series of palace complexes. The glass fused and worked there was presumably for local as well as for regional consumption. Al‐Raqqa currently appears to have produced the earliest well‐dated production on record in the Middle East of an Islamic high‐magnesia glass based on an alkaline plant ash flux and quartz. An eighth to ninth century late ‘Roman’/Byzantine soda–lime recipe of natron and sand begins to be replaced in the eighth to ninth century by a plant ash – quartz Islamic soda–lime composition. By the 11th century, this process was nearly complete. The early Islamic natron glass compositional group from al‐Raqqa shows very little spread in values, indicating a repeatedly well‐controlled process with the use of chemically homogeneous raw materials. A compositionally more diffuse range of eighth to ninth century plant ash glass compositions have been identified. One is not only distinct from established groups of plant ash and natron glasses, but is believed to be the result of experimentation with new raw material combinations. Compositional analysis of primary production waste including furnace glass (raw glass adhering to furnace brick) shows that contemporary glasses of three distinct plant ash types based on various combinations of plant ash, quartz and sand were being made in al‐Raqqa during the late eighth to ninth centuries. This is a uniquely wide compositional range from an ancient glass production site, offering new insights into the complexity of Islamic glass technology at a time of change and innovation.     

COOKING AND PAINTED WARE FROM SAN GIUSTO (LUCERA,FOGGIA): THE PRODUCTION CYCLE,FROM THE SUPPLY OF RAW MATERIALS TO THE COMMERCIALIZATION OF PRODUCTS*

Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro‐Raman spectroscopy, X‐ray diffraction, X‐ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historical–archaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600–750°C for cooking ware; 850–1050°C for painted ware).     

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.     

Freezing and melting behaviors of H2O‐NaCl‐CaCl2 solutions in fused silica capillaries and glass‐sandwiched films: implications for fluid inclusion studies

Fluid inclusions of the H₂O‐NaCl‐CaCl₂ system are notorious for their metastable behavior during cooling and heating processes, which can render microthermometric measurement impossible or difficult and interpretation of the results ambiguous. This study addresses these problems through detailed microscopic examination of synthetic solutions during cooling and warming runs, development of methods to enhance nucleation of hydrates, and comparison of microthermometric results with different degrees of metastability with values predicted for stable conditions. Synthetic H₂O‐NaCl‐CaCl₂ solutions with different NaCl/(NaCl + CaCl₂) ratios were prepared and loaded in fused silica capillaries and glass‐sandwiched films for microthermometric studies; pure solutions were used with the capillaries to simulate fluid inclusions, whereas alumina powder was added in the solutions to facilitate ice and hydrate crystallization in the sandwiched samples. The phase changes observed and the microthermometric data obtained in this study have led to the following conclusions that have important implications for fluid inclusion studies: (i) most H₂O‐NaCl‐CaCl₂ inclusions that appear to be completely frozen in the first cooling run to ?185°C actually contain large amounts of residual solution, as also reported in some previous studies; (ii) inability of H₂O‐NaCl‐CaCl₂ inclusions to freeze completely may be related to their composition (low NaCl/(NaCl + CaCl₂) ratios) and lack of solid particles; (iii) crystallization of hydrates, which is important for cryogenic Raman spectroscopic studies of fluid inclusion composition, can be greatly enhanced by finding an optimum combination of cooling and warming rates and temperatures; and (iv) even if an inclusion is not completely frozen, the melting temperatures of hydrohalite and ice are still valid for estimating the fluid composition.     

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.     

Origin of palaeofluids in a normal fault setting in the Aegean region

The province of Burdur (SW Turkey) is seismically an active region. A structural, geochronological, petrographical, geochemical and fluid inclusion study of extension veins and fault‐related calcite precipitates has been undertaken to reconstruct the palaeofluid flow pattern in this normal fault setting in the Aegean region. A palaeostress analysis and U/Th dating of the precipitates reveals the neotectonic significance of the sampled calcites. Fluid inclusion microthermometry of calcites‐filling extension veins shows final melting temperatures (T_m ice) of 0°C. This indicates pure water, most likely of meteoric origin. The oxygen isotope values (?9.8‰ to ?6.5‰ VPDB) and the carbon isotopic composition (?10.4‰ to ?2.9‰ VPDB) of these calcites also show a near‐surface meteoric origin of the fluid responsible for precipitation. The microstructural characteristics of fault‐related calcites indicate that calcite precipitation was linked with fault activity. Final melting temperature of fault‐related calcites ranges between 0 and ?1.9°C. The oxygen isotope values show a broad range between ?15.0‰ and ?2.2‰ VPDB. Several of these calcites have a δ¹⁸O composition that is higher or lower than the oxygen isotopic composition of meteoric calcites in the area (i.e. between ?10‰ and ?6‰ VPDB). The δ¹³C composition largely falls within the range of the host limestones and reflects a rock‐buffered system. Microthermometry and stable isotopic study indicate a meteoric origin of the fluids with some degree of water–rock interaction or mixing with another fluid. Temperatures deduced from microthermometry and stable isotope analyses indicate precipitation temperatures around 50°C. These higher temperatures and the evidence for water–rock interaction indicate a flow path long enough to equilibrate with the host–rock limestone and to increase the temperature. The combined study of extension vein‐ and fault‐related calcite precipitates enables determining the origin of the fluids responsible for precipitation in a normal fault setting. Meteoric water infiltrated in the limestones to a depth of at least 1 km and underwent water–rock interaction or mixing with a residual fluid. This fluid was, moreover, tapped during fault activity. The extension veins, on the contrary, were passively filled with calcites precipitating from the downwards‐migrating meteoric water.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

COAL AND CREMATION AT THE TSCHUDI BURN,CHAN CHAN,NORTHERN PERU*

Analyses of a 20–30 cm thick, completely combusted ash at the 25 × 70 m Tschudi burn at Chan Chan, northern Perú, contain 52–55 wt% SiO₂, 180–210 ppm zirconium and are consistent with coal ash. Soil geochemistry across the burn showed elevated calcium and phosphorus content, possible evidence for reported human cremation. A calcined, 5 g, 4.5 cm skull fragment recovered from the burn was confirmed as human by protein radioimmunoassay (pRIA). X‐ray diffraction showed that the bone had been heated to 520°C. The burn took place c. ad 1312–1438 based on interpretation of a ¹⁴C date on carbonized plant tinder.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

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.     

Variabilité et fréquence des cycles de gel‐dégel dans la région de Québec, 1977–2006

Freeze‐thaw cycles are most common at the beginning or near the end of the winter season. These cycles have various effects on the ecosystems of Eastern Canada, affecting both biotic and abiotic components of temperate cold environments. Using air temperature minima and maxima from four meteorological stations close to Québec City, we determined the frequency of daily freeze‐thaw cycles for the last 30 years. The results show no significant increase in the number of freeze‐thaw cycles despite a small increase in air temperature. Polynomial curves describing the relationship between mean air temperatures and the number of freeze‐thaw cycles were calculated. Based on these equations and anticipating a climate change scenario, we projected future freeze‐thaw cycles. Assuming a 5 °C increase in mean air temperatures by 2100, we estimated that the number of days with a freeze‐thaw cycle could increase by approximately 20 days per winter. The increase in the number of such cycles will be concentrated during the coldest months of the winter (January and February).     

DETECTING AND QUANTIFYING HEAT TREATMENT OF FLINT AND OTHER SILICA ROCKS: A NEW NON‐DESTRUCTIVE METHOD APPLIED TO HEAT‐TREATED FLINT FROM THE NEOLITHIC CHASSEY CULTURE,SOUTHERN FRANCE

Heat treatment of lithic raw material is known from the Middle Stone Age to the Neolithic. These findings require archaeometric techniques and methods for detecting the heat‐induced effects within lithic artefacts. However, the existing methods are often cost‐intensive and time‐consuming, and most of them are destructive. Here, we present a new method using the infrared spectroscopic measurement of the strength of H‐bonds formed between surface silanole groups (SiOH) and H₂O molecules held in open pores of the samples. The reduction of H‐bond strength in chalcedony is shown to be strongly correlated with the loss of open pores induced by heat treatment. Hence, the method is based on measuring one of the transformations aimed for by the instigators of the heat treatment: the reduction of porosity that modifies the rock's mechanical properties. A first application to heat‐treated material from the Neolithic Chassey culture (southern France) shows that flint was heated to temperatures between 200°C and 250°C in this period. This has important implications for the study of the procedures used and the heating environments. Our new method is non‐destructive, rapid, cost‐effective and allows for detection of the used annealing temperatures.     

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.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.