An attempt to estimate firing temperature using OSL pre-dose sensitization of quartz

The estimation of firing temperature of ceramics using methods based on pre-dose sensitization of the 110°C TL peak of quartz have yielded incoherent results. Recently the fast component of the CW-OSL of quartz has been observed to have pre-dose characteristics similar to that of the 110°C TL peak. The motivation for this study has been to look into the feasibility of this signal, the OSL counter part of pre-dosed TL emission, for the firing temperature identification. The variation in the sensitization ratio of the TL and OSL emissions with different heating temperatures was also utilized to unveil the firing temperature mark of the specimen.     

Firing Techniques of the Impasti from the Protohistoric Site of Concordia Sagittaria (Venice)

⁵⁷Fe Mössbauer spectroscopy provided relevant information on the firing techniques employed in manufacturing concotto and coarse pottery, two types of fired clay mixtures (impasti) of the protohistoric settlement site of Concordia Sagittaria. The firing techniques of Concordia were reconstructed by comparing the Mössbauer patterns of the artefacts with those of the local raw clays fired in the laboratory. The concotto was produced in kilns by firing clay mixtures under oxidizing conditions at 700–1000°C, or at lower temperatures in the open air. The firing of these clay mixtures containing mainly ground pieces of waste pottery, resulted in hard and variously coloured construction materials, particularly suitable for humid environments. In turn, the coarse pottery was produced by firing clay mixtures more homogeneous than those used for the artefacts of concotto. The firing of coarse pottery was performed under reducing conditions at about 900°C with a final exposure to air by opening the hot kiln. Light and agreeable coarse pottery, with a red surface on the grey-black core, was obtained when the effective temperature of air was higher than 500°C.     

Roman traces in Germania magna: New thermoluminescence and pIRIR290 data from a lime kiln at Bergisch Gladbach,Germany

The applicability of a post‐infrared infrared stimulated luminescence (pIRIR₂₉₀) protocol and two different thermoluminescence (TL) protocols—a single aliquot regeneration (SAR) and a multiple aliquot additive dose (MAAD)—was tested on six polymineral fine‐grain (4–11 μm) samples extracted from the wall remains of a Roman lime kiln and a Roman roof tile. These remains had been excavated close to Bergisch Gladbach, which was at that time part of Germania magna. For the pIRIR₂₉₀ measurements, no dependence of D_e on first‐stimulation temperature was detectable, and the standard first stimulation temperature at 50°C was adopted. Fading tests and dose‐recovery tests were made for all samples. Background subtracted glow curves were recorded up to 480°C for TL after a preheat of 220°C for 120 s. A‐values were determined for all TL and pIRIR measurements. The results for all three protocols were fairly consistent, and TL and pIRIR₂₉₀ protocols are shown to be suitable to estimate reliable equivalent doses for the fired kiln walls. The resulting ages are in agreement with the expected time range—Roman Iron Age—and with independent age control provided by radiocarbon ages of animal bones and charcoal from the firing chamber.     

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.     

Changes in natural OSL sensitivity during single aliquot regeneration procedure and their implications for equivalent dose determination

Measurement of low temperature (90°C–120°C) Thermoluminescence (TL) sensitivity of natural quartz samples subjected to pre-heating and optical stimulation indicate that significant sensitivity changes can occur during measurement of the natural Optically Stimulated Luminescence (OSL). During the measurement of natural signal, the luminescence sensitivity of samples can change by 40%. The sensitivity changes both during the initial preheat and the measurement of natural OSL. The currently used version of Single Aliquot Regeneration (SAR) protocol measures and corrects for the sensitivity changes after preheat and readout of natural OSL. However, it does not take into account the changes in sensitivity during the readout of the natural signal. We therefore developed a correction procedure so that both the natural and the regenerated OSL intensities can be measured and plotted with the same sensitivity and suggest that in the absence of such a correction, a considerable fraction of the SAR based ages could have systematic errors. The correction for the sensitivity is based on the use of sensitivity of 110°C TL quartz peak, which is correlated to OSL signal (Murray and Roberts, 1998). The use of 110°C peak provides a reasonable measure of the changes in OSL sensitivity of quartz. A modified Natural Sensitivity Corrected-SAR (NSC-SAR) procedure, that comprises the measurement of, 1) the TL intensity of 110°C peak for a test dose on sample as received (i.e. natural sample) and, 2) the sensitivity of the 110°C peak of the same sample after the preheat and read out of the natural OSL, is proposed. This ratio, termed as Natural Correction Factor (NCF), then provides a way to correct for sensitivity changes. Results on samples from diverse depositional environments indicated that the NSC-SAR consistently (without exception) provided improved distribution in paleodoses i.e. a lower scatter compared to the standard SAR protocol. In addition, the use of this protocol also resolved anomalous cases where the intensity of natural OSL was significantly above the saturation intensity of the regenerated OSL. Implicitly, this study implies a caution on the use of palaeodoses obtained from single grains as such a correction is not possible in the currently used automated single grain OSL measurement systems. The only way now on will be to analyze aliquots with only a grain on them.     

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.     

THE PRE-DOSE TECHNIQUE: A NEW THERMO-LUMINESCENT DATING METHOD

A thermoluminescent (TL) glow-curve peak occurs around 110°C for the mineral quartz. Its sensitivity may be changed by application of a radiation dose (termed the pre-dose) followed by a heating of the quartz to 500°C: heating alone causes no sensitivity change. The enhancement observed (measured relative to the sensitivity of the peak prior to heating) is a measure of the magnitude of the pre-dose. For quartz extracted from pottery the sensitivity enhancement induced by laboratory heating records a natural pre-dose, i.e. the accumulated dose experienced during archaeological burial. The latter quantity is used in TL age-determination and a test programme is reported on the application of the pre-dose dating method to sites covering the Roman era in Britain forward to modern times.     

Behavior of various Nigerian quartz samples to repeated irradiation and heating

In the present work the sensitization of the entire glow-curve is studied in 6 different quartz samples of Nigerian origin. The investigation was applied to the un-fired “as is” samples as well as to samples fired at 900°C for 1 hour following cooling to room temperature. The results showed that in the case of “as is” glow-curve is sensitized as a whole. There is an abrupt transition from the “natural” sensitivity without any previous heating and the artificial sensitivity induced after the first heating. The sensitization is growing up strongly to the 10^th heating but to a lower rate. The sensitization factor of the TL glow-peak at “110°C” was found to be linearly correlated to the higher temperature TL peaks. In the case of annealed samples there is an initial increase between the sensitivity immediately after the end of annealing and after the first heating. As the number of heating is increased up to the 10^th heating the sensitization is stabilized at a constant value. The results are discussed in the frame-work of existing models and implications of the sensitization effect in various applications, while some explanations are attempted.     

The Firing Temperature of Pottery from Ancient Mesopotamia,Turkey, Using Luminescence Methods: A Case Study for Different Grain‐Size Fractions

The assessment of the firing temperature of a prehistoric pottery sample collected from ancient Mesopotamia, Turkey was studied using luminescence techniques. The methods for this estimation involved the observation of the thermal and pre‐dose sensitization with various re‐firing temperatures for both TL and the OSL signals. In the former case, the 110°C TL peak and the rest of the glow curve were used as proxies in this study. In the framework of a first attempt to investigate the impact of grain‐size dependence on the sensitization of the luminescence signals, the aforementioned study was performed with four different pottery grain‐size fractions: (i) less than 60 μm, (ii) 60–90 μm, (iii) 90–180 μm and (iv) 180–250 μm. The results clearly demonstrated the firing temperature mark of ～500°C in for the grain size of 90–180 μm, while—as in the case of the lower grain‐size fraction—a third proxy, the ratio of the pre‐dosed to the thermal sensitization, was seen to indicate the firing temperature. The remaining two grain‐size fractions failed to provide any meaningful results with regard to the firing temperature estimation. The dependence of the TL characteristics on the grain size was explained in the framework of the mixed mineralogy.     

ON THE USE OF COLOUR COORDINATES TO EVALUATE FIRING TEMPERATURES OF ANCIENT POTTERY*

Colour measurement was investigated as a means to evaluate equivalent firing temperatures of ancient pottery. Colour coordinates were determined on samples of six clays previously fired, and then refired, in the temperature range 600–1100°C. Under the adopted conditions, significant variations of colour hue and saturation were normally observed on refired samples only after the original firing temperature had been exceeded; less reliable information was provided by luminosity. Original firing temperatures of clay samples were correctly recognized in most cases by projecting the points representing samples’ colour on to the a*b* plane of the ClEL*a*b* colour space.     

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.     

MINERALOGICAL INVESTIGATIONS OF MEDIEVAL BRICK SAMPLES FROM BÉKÉS COUNTY (SE HUNGARY)

Brick samples from nine archaeological sites representing seven contemporary medieval settlements in Békés County (SE Hungary) were analysed by quantitative X‐ray powder diffraction, optical microscopic, scanning electron microscopic and coupled thermal analytical – evolved gas analytical methods. The aims of this study were to give a mineralogical–petrographical characterization of the brick samples, to gain possible information on the raw clay and the admixed materials, and to determine the firing techniques applied in medieval southeastern Hungary. The mineralogical composition of the samples suggests that the locally extracted clay was mixed with fluvial sand and wheat (Triticum monococcum L.) chaff. The moulded bricks were fired in clamps. The different degrees of calcite consumption suggest that the firing temperature ranged from ～750°C to ～950°C. Moreover, the well‐developed reaction coronas on calcite grains indicate long firing times, lasting perhaps several days.     

Anomalous fading and crystalline structure: Studies on individual chondrules from the same parent body

Plagioclase feldspar is the major luminescent mineral in meteorites. Thermoluminescence (TL) characteristics, peak temperature (T_m), full width at half maximum (FWHM), ratio of high (HT) to low temperature (LT) peak, and TL sensitivity (TL/dose/mass) to an extent reflect degree of crystallinity of the mineral. The present study explores and establishes a correlation between quantum mechanical anomalous (athermal) fading and structural state by examining TL of individual chondrules. Chondrules were separated using freeze-thaw technique from a single fragment of Dhajala meteorite. The results show large variation in T_m (155?230°C), FWHM (80?210°C) and HT/LT (0.07–0.47) and seem to be positively correlated. TL sensitivity (ranging from 14 to 554 counts/s/Gy/mg) decreases with increasing T_m and FWHM. Large variations in TL parameters (Tm, FWHM, HT/LT, and Sensitivty) suggest that individual chondrules had different degree of crystallization. Thermal annealing experiments suggest that comparatively ordered form of feldspar can be converted to a disordered form by annealing the sample at high temperatures (1000°C) for long time (10 hr) in vacuum (1 mbar pressure) condition and rapidly cooling it. Measured anomalous fading suggest that fading rate increases as the crystal form changes from an ordered state to a disordered state. However, the fading rate becomes nearly negligible for the most disordered feldspars.     

FOCUS: Provenance of Ceramics Revealed by Magnetic Susceptibility and Thermoluminescence

A new method for provenance determination of ceramics is presented. The samples were measured for magnetic susceptibility and for the TL intensity produced by artificially induced radiation in a pre-heated sample. Characteristic differences in magnetic susceptibility and TL sensitivity were found to exist between different clay sources, and in a diagram of susceptibility versus TL intensity, ceramics of different provenances often plot in distinctly different areas. Samples of 0·01–1 g of burnt clay were used. The method has been tested on a dozen archaeological sites, three of which are presented here as examples. Choice of tempering material, firing temperature, and oxygen tension during firing affect the susceptibility and the TL signals somewhat, and these effects have been tested experimentally.     

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.     

Pottery firing temperatures: a new method for determining the firing temperature of ceramics and burnt clay

A new method for determining the maximum firing temperature of ceramics and burnt clay is presented. The technique relies on measuring the magnetic susceptibility on a step-wise re-fired sample. The validity of the method has been tested by determining firing temperatures of two sets of clay samples fired at temperatures ranging from 400 to 1000 °C. Aliquots of the same samples have been studied petrographically by optical microscopy on thin sections and analyzed by powder X-ray diffraction in order to monitor structural and mineralogical changes as a function of temperature. The method is demonstrated on samples from four geographically widely different sites and it is applied to a larger set of ceramics of Late (ca. AD 900–AD 1450) and Inca (ca. AD 1480–AD 1532) periods from the Northwestern Argentine region, dating to a limited period of time prior to the fall of the Inca Empire. The method is shown to be a powerful tool in revealing archaeological information about the change in firing technologies in the pre-Hispanic societies in the Andean area through time.     

Technological examination of Neolithic-Bronze Age pottery from central and southeast Europe and from the Near East

Scanning electron microscopy is used to examine sequences of pottery sherds from central and southeast Europe, Greece and the Near East spanning the period from the Neolithic to the Bronze Age, in order to obtain information on the ceramic technologies employed in antiquity. On the basis of the vitrification observed and the chemical composition, the types of clay and firing procedures (temperature and atmosphere) employed in the manufacture of the pottery are defined. Two under-lying trends in the associated ceramic technologies are thus identified. The first is based on the use of non-calcareous or “unstable” calcareous clays fired in a reducing atmosphere at temperatures below 800 °C and the second on the use of “stable” calcareous clays fired in an oxidizing atmosphere at temperatures in excess of 800 °C.     

Kinetic analysis of thermoluminescence glow curves in feldspar: evidence for a continuous distribution of energies

The thermoluminescence (TL) glow curves from feldspars have been the subject of numerous studies, because of their importance in luminescence dating and dosimetry. This paper presents new experimental TL glow curves in a plagioclase feldspar, measured using the T _max-T _stop technique of glow curve analysis. Kinetic analysis of the experimental results is carried out for a freshly irradiated sample, as well as for a sample which has undergone optical treatment using infrared light for 100 s at 50°C. Application of the initial rise method of analysis indicates that the TL signals from both samples can be characterized by a continuous distribution of energy levels. By subtracting the TL glow curves measured at successive T _stop values, a series of TL glow curves is obtained which are analyzed using the empirical general order kinetics. It is found that all TL glow curves obtained by this subtractive procedure can be described accurately by the same general order parameter b ～1.7. In a second attempt to analyze the same TL glow curves and possibly extract information about the underlying luminescence process, the shape of TL glow curves is analyzed using a recently proposed physical kinetic model which describes localized electronic recombination in donor-acceptor pairs. Within this model, recombination is assumed to take place via the excited state of the donor, and nearest-neighbor recombinations take place within a random distribution of centers. This recent model has been used recently to describe successfully several types of luminescence signals. This paper shows that it is possible to obtain good fits to the experimental data using either one of these two approaches.     

Petroleum infiltration of high-grade basement, South Norway: Pressure-Temperature-time-composition (P–T–t–X) constraints

Fluid inclusion data provide pressure–temperature–time–composition (P–T–t–X) constraints for an episode of petroleum infiltration of the crystalline basement in South Norway. Petroleum inclusions associated with pyrobitumen occur in postmetamorphic quartz veins in the Modum Complex. Three groups of fluid compositions have been shown, ranging from CH₄ ± CO₂ to condensates with alkanes up to C₁₅. The range in fluid composition is a result of petroleum decomposition at high temperature. Globular and massive pyrobitumen occurs in the quartz veins or in associated vein systems. Reflectance (%Rm) measurements of 3.20–3.35 correspond to a maximum temperature of 207–214°C for the pyrobitumen associated with group II and III inclusions. Geothermometry of chlorites included in the quartz show results of 226–231°C. Pressure conditions of trapping for all three groups of inclusion fluids have been estimated to 520–985 bar at 220°C. The pressure range is probably a result of fluctuations caused by repeated fracture opening and sealing due to seismic activity coupled with mineral growth. A lack of systematic textural relationships between the three groups of inclusions and similar pressure–temperature estimates for all fluid types indicate trapping at similar times and a process of rapid change. Fluid migration in fractures from an overlying, overpressured sedimentary basin into a dry, crystalline basement best explains the observed P–T–t–X constraints.