Stable carbon and oxygen isotopic compositions of wood ash: an experimental study with archaeological implications

Wood ash, composed mainly of the mineral calcite, is an important component in many archaeological sites. Identification of wood ash in the archaeological record is often difficult due to mixing of ash with other calcitic components of geogenic origin and/or due to diagenetic changes. A recent empirical study using the stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in wood ash enabled the identification of mixtures of wood ash with geogenic calcite and to follow diagenetic changes due to partial dissolution and re-precipitation of ash in two prehistoric cave sites in Israel. Little however is known about the processes responsible for the isotopic compositions of wood ash in relation to formation at various temperatures and the influence on isotopic composition of ash from a variety of plant species. Here we present an experimental study of wood ash formed by burning three C3 tree species and one C4 desert bush at different temperatures. The results indicate that there are significant differences in the isotopic compositions of carbon and oxygen between wood ash that forms by combustion at a relatively low temperature (500 °C) and at a higher temperature (900 °C). In addition, we show that the isotopic composition of carbon and oxygen in high temperature wood ash approaches equilibrium over a period of several months and that the carbon isotopic composition of low temperature wood ash may reflect the photosynthetic pathway of the burnt woody species. Lastly, we show that the isotopic compositions obtained from wood ash prepared at different temperatures do not reflect a temperature dependent fractionation process, but a mixing line between calcite that formed by low temperature combustion and calcite formed by high temperature combustion which later underwent re-carbonation with atmospheric CO₂. In addition, we suggest that exchange processes may possibly occur during combustion between decomposing calcium-oxalate and atmospheric O₂, CO₂ and CO. The archaeological implications of this study are discussed in relation to identification of wood ash in the archaeological record, identification of fuel sources and burning temperatures, and diagenetic changes expected in karstic cave environments. The method presented here can be applied at any archaeological site.     

Distinguishing between calcites formed by different mechanisms using infrared spectrometry: archaeological applications

Infrared spectrometry is a well-established method for the identification of minerals. Due to its simplicity and the short time required to obtain a result, it can be practiced on-site during excavation using portable infrared spectrometers. However, the identification of a mineral may not be sufficient. For example, a lime plaster floor and a crushed chalk surface have a similar appearance and are composed of the same mineral – calcite. Here we exploit differences in the infrared spectra of geogenic, biogenic and pyrogenic calcites for the identification of each calcite type. The infrared calcite spectrum has three characteristic peaks in the region of 400–4000 cm⁻¹, designated ν₂, ν₃, and ν₄. When a calcite sample is ground, as part of the measurement preparation procedure, some grinding dependent changes will be revealed in the infrared spectrum. With additional grinding, the ν₃ peak narrows and the heights of the ν₂ and ν₄ peaks decrease, when both are normalized to the ν₃ height. By plotting the normalized heights of the ν₂versus the ν₄ of several grindings of the same sample, a characteristic trend line is formed for each calcite type. The trend lines of geogenic calcites have the shallowest slopes and highest ν₄ values when compared to pyrogenic calcites, which can be further divided to ash and plaster/mortar samples. This method can assist in distinguishing between the various calcites, and provide insights into homogeneity and preservation state of the calcitic materials in question.     

Iron Age hydraulic plaster from Tell es-Safi/Gath,Israel

Hydraulic plasters or mortars prior to the Roman period are rare. Here, we report the identification and characterization of 3000 year old (Iron Age) hydraulic plaster surfaces from the site of Tell es-Safi/Gath. This site, located in central Israel, was occupied almost continuously from prehistoric through modern times, and is identified as the Canaanite and Philistine city of Gath. A survey using an on-site Fourier transform infrared spectrometer (FTIR) identified the presence of amorphous silicates, in addition to calcite, in each of two superimposed plaster layers. This suite of minerals is characteristic of hydraulic plaster. An in-depth characterization of the plasters using FTIR, acid dissolution, X-ray fluorescence (XRF), X-ray powder diffractometry (pXRD), heating experiments and scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM–EDS), shows that special silicate-containing minerals were brought from some distance to the site in order to produce these plaster surfaces. We therefore conclude that the plasters were deliberately produced, and were not the result of a fortuitous addition of local silicate minerals. A layer of around 150 μm thick enriched in carbonate hydroxylapatite was found in both plaster surfaces, and the same mineral was identified by infrared spectrometry in the surrounding sediments. This suggests that organic materials were used on these surfaces. These surfaces are among the oldest hydraulic plasters known.     

石质文物加固中细菌诱导碳酸钙生成的研究

为探讨细菌生物矿化法加固石质文物,利用枯草杆菌-Ⅱ在特殊含钙培养基上进行诱导矿化研究.结果表明,筛选出的菌株枯草杆菌-Ⅱ在M-3+ASP固体和液体培养基上能诱导生成白色物;白色诱导物经X-衍射分析为碳酸钙;电子显微镜下观察发现碳酸钙在细菌周围生成,并包裹细菌菌体,使细菌菌体钙化.     

陕西旬邑西头遗址出土彩绘白灰面的成分和工艺分析

对陕西旬邑县西头遗址出土的彩绘白灰面进行了成分和制作工艺分析。采用偏光显微分析、扫描电镜能谱、X射线衍射,拉曼光谱分析了该彩绘面的颜料和石灰层成分,采用气相色谱-质谱联用技术(GC-MS)分析了该彩绘面的胶料成分。结果表明,该彩绘面的颜料由铁红,铁黄和绿土构成。白灰层由碳酸钙构成,部分样品中存在双层白灰层。GC-MS分析表明,该彩绘面的胶料含动物胶,可能还含蛋类。通过比较研究发现,旬邑彩绘白灰面的制作工艺和与后期壁画制作工艺相似,对其组成和工艺的研究将有助于探索先周时期关中地区壁画的起源和发展。     

Investigation of lime mortars and plasters from archaeological excavations in Hippos (Israel) using Electron Paramagnetic Resonance

This study presents the preliminary results of investigation of the lime mortars and plasters from archaeological excavations in Hippos (Israel), using Electron Paramagnetic Resonance (EPR) spectroscopy. The research was conducted in order to characterize the building material and its reaction to ionizing radiation. The ancient settlement Hippos, situated on the east shore of the Sea of Galilee, functioned from the 3^rd cent. BC until it was destroyed by the earthquake in 749 AD. Lime mortars and plasters show carbonate and locally gypsum character of binder and different kind of aggregate. Samples were γ-irradiated and measured using X-band EPR spectrometer. Computer Resolution Enhancement Method was applied to the complex spectra. Some of the γ-induced EPR signals were attributed to CO₂ ^? and CO₃ ^3? paramagnetic centres. Exponential growth of the dose response curve above 1 kGy and saturation for doses above 20 kGy was observed. For doses lower than 1 kGy the dose response curve has a linear character. The presence of γ-sensitive carbonate paramagnetic centres could indicate that, after further studies, well-chosen samples of mortars and plasters might be suitable for EPR dating, assuming the centres have been sufficiently bleached during the manufacturing process.     

Characterization of lime carbonates in plasters from Teotihuacan,Mexico: preliminary results of cathodoluminescence and carbon isotope analyses

This study characterizes the degree of calcination of lime in lime plaster samples from Teotihuacan, the capital of a regional state in prehispanic Central Mexico. Lime plaster production consists of multiple steps, from the firing of raw materials to the mixing of lime and aggregate and the final application. While previous studies have focused on the compositional variability, specifically the recipe of lime plasters and mortars, the characterization of lime itself has not been sufficiently addressed. In this study, cathodoluminescence analysis coupled with petrographic and image analyses were employed to examine the degree of calcination of lime. The results of cathodoluminescence petrography were further examined through stable carbon isotope and ¹⁴C measurements. It appeared that the results of cathodoluminescence analysis are consistent with those of other analytical methods and that there are diachronic changes in the degree of calcination of lime among lime plaster samples. This implies changes in the organization of lime production, specifically the consistency in the control of firing temperature.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.     

Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments

Oscillatory zoning and fine‐scale variations in trace element chemistry are commonly observed in hydrothermal minerals. It has been suggested that fine‐scale chemical variations are caused by extrinsic changes in the parent hydrothermal system, such as varying fluid composition, pressure or temperature, as well as changes in mineral growth rate. In this study, LA–ICP–MS (laser ablation, inductively coupled plasma mass spectrometer) analyses were carried out on calcite crystals grown in Ca–NH₃–Cl solutions doped with rare earth elements (REE). The variety of crystal morphologies observed (euhedral to acicular), likely relate to variations in trace element abundance and calcite supersaturation state. Crystals display oscillatory and sector zoning, with significant variations in REE concentrations among zones. Cyclic variations in REE concentrations (exceeding 10‐fold) occur over distances of <1 mm along the growth direction of acicular calcite crystals. In general, trace element concentrations decrease during progressive crystal growth, implying that the concentration of trace and REEs within crystals reflects the overall composition of the growth solution. However, bulk changes in crystal composition are modulated by fine‐scale (<1 mm) variations, which are inferred to be caused by growth‐rate‐controlled incorporation of trace elements. These results have important implications for using hydrothermal minerals to infer fluctuations in fluid compositions in ancient, exhumed hydrothermal systems.     

The Beginnings of Pyrotechnology: Neolithic and Egyptian Lime Plaster

Abstract

Characterization of pre-pottery Neolithic and Egyptian plasters has been carried out, with emphasis on microstructural observations with the scanning electron microscope. Samples from Asikli Hüyük, Çayönü Tepesi, Tell Ramad, and Jericho were examined; the results show that true lime plasters were utilized in the aceramic Neolithic. The quantity of material used and the temperature necessary for limestone calcination imply that some sort of crude kilns must have been employed. The availability of this technology makes understandable the subsequent rapid development of fired pottery. Samples of Egyptian plaster from Timna (ca. 1400–1200 B.C.) were found to be lime, contradicting Lucas' statement that lime plasters were unknown in Egypt prior to the Ptolemaic period. Gypsum plasters of both Neolithic and Egyptian origin have also been characterized.     

Biofilm growth in human skeletal material from ancient Mesopotamia

Investigators have long recognised the effects of microbial activity on archaeological bone. These investigators, however, have focused on single or groups of microbes rather than on complex microbial aggregates such as biofilms, a focus that has affected our understanding of archaeological bone biodeterioration. In this paper, we report on the investigation of a biofilm in archaeological human bone from the site of Tell Leilan, Syria (2900–1900 BCE). Scanning electron microscopy indicated that the biofilm is characterised by single cells and microcolonies of bacteria and fungi, as well as calcite crystals that were all embedded within extracellular polymeric substances. Using culture techniques and DNA sequencing, we isolated and identified several microbes from the biofilm including Amycolatopsis sp., Penicillium chrysogenum, Aspergillus sp., Chaetomium sp., and Cladosporium sp. Having characterised the Leilan biofilm, we are now closer to understanding the complex process of bone biodeterioration in archaeological bone collections.     

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

Special Studies: Petrographic Thin Sections and the Development of Neolithic Plaster Production in Northern Israel

Abstract

Petrographic and petrological techniques have been used to examine Neolithic plaster products from several sites in northern Israel. Referring to former studies, the value of different analytical methods for the examination of ancient plasters and mortars is considered. The new data, achieved by the relatively simple method of Petrographic examination, reveal a different interpretation of Neolithic craft specialization and cultural interchange. The production methods of architectural plasters, together with plaster products (e.g., beads, figurines, “white ware” vessels, etc.), differ significantly between sites, even in the limited region of the Israeli Galilee. In most cases, burnt lime was used as a secondary raw material, together with powdered chalk, sand, and clay. In our view, lime burning was a casual, limited activity that did not require intensive labor. Therefore, fulltime specialists would not have been required and, what is more, the complexity of Neolithic society, based on considerations of plaster technology, has yet to be clearly demonstrated.     

Effects of pore fluid flow and chemistry on compaction creep of calcite by pressure solution at 150°C

Uni‐axial compaction creep experiments were performed on crushed limestone and analytical grade calcite powders at 150°C, a pore fluid pressure of 20 MPa, and effective axial stresses of 30 and 40 MPa. Previous experiments have shown that compaction under these conditions is dominated by intergranular pressure solution (IPS). The aim of the present tests was to determine the inter‐relationship between pore fluid chemistry, compaction rate and the rate‐controlling process of IPS. Intermittent flow‐through runs conducted using CaCO₃ solution showed no effect on creep rate at low strains (<4–5%) but a major acceleration at high strains (5–10%). Measurements of the Ca concentration present in fluid samples revealed the build‐up of a high super‐saturation of CaCO₃ during compaction under zero flow conditions, especially at high strains. Active flow‐through led to a drop in Ca concentration, which corresponded with creep acceleration. Addition of NaCl to the pore fluid, at a concentration of 0.5 m , increased the creep rate of the analytical grade calcite samples roughly in proportion to the enhancement of calcite solubility. Addition of Mg²⁺ and to the pore fluid, in concentrations of 0.05 and 0.001 m, respectively, caused major retardation of compaction creep. Integrating our mechanical, flow‐through and chemical data points strongly to diffusion‐controlled IPS being the dominant deformation mechanism in the calcite‐water system under closed‐system (zero flow) conditions at low strains (<4–5%), giving way to precipitation control at higher strains. Our fluid composition data suggest that this transition is because of accumulation of impurities in the pore fluid. As Mg²⁺ and phosphate ions are common in natural pore fluids, it is likely that retarded precipitation will be the rate‐limiting step of IPS in carbonates in nature. To quantify diagenetic compaction and porosity‐permeability reduction rates by IPS in carbonates needs to account for this.     

Magnetite grain-size analysis and sourcing of Mediterranean obsidians

The potential of magnetic grain-size variations as an obsidian source characteristic is investigated using geological and archaeological obsidians from five islands of the Mediterranean Sea: Lipari, Sardinia, Palmarola, Pantelleria, Melos. Four parameters are used: magnetic (χ) and anhysteretic (χ_a) susceptibilities, saturation isothermal remanent magnetizations at room (SIRM₂₉₃) and liquid nitrogen (SIRM₇₇) temperature. The ratio S_T = SIRM₇₇/SIRM₂₉₃, which depends on the superparamagnetic grains relative abundance, varies little in each individual site, with the exception of Lipari which is characterized by large variations and the highest content of superparamagnetic grains. The χ_a vs. χ plot ( King et al., 1982) shows some within-site dispersion of the samples; but the ratio Q_a = χ_a/χ, which is strongly influenced by the single domain grains content, is characteristic for each site. The combined use of the King and Q_a vs. S_T plots discriminates the samples from most of the sites and suggests that the grain-size analysis is a promising approach in sourcing obsidian archaeological artefacts. Moreover, the measurements of the four parameters used are simple, quick and feasible with no or little damage to archaeological finds.     

The geochronological potential of isoleucine epimerisation in cassowary and megapode eggshells from archaeological sites

Our research demonstrates that the extent of isoleucine epimerisation (A/I) in fragments of avian eggshells provides geochronological information in archaeological contexts. In the archaeological sequence of Hay Cave, northern Queensland, Australia, there is an excellent correspondence between the A/I values of Australian brush-turkey (Alectura lathami) eggshells (n = 99) and independent geochronological control (n = 16 radiocarbon ages including 4 on eggshell calcite). The A/I values identify three phases of deposition during the Holocene at Hay Cave. In contrast to the Alectura eggshell A/I values, a poor correspondence was observed between the A/I values of cassowary (Casuarius) eggshells from Toé (n = 35) and Kria caves (n = 23) (Ayamaru Plateau, Papua) and the depths from which the specimens were recovered in these stratified sequences. Given coherent archaeofauna trends and radiocarbon chronologies (n = 8 and 2 eggshell calcite radiocarbon ages at Toé and Kria, respectively) with respect to depth, the variable A/I values are not explicable in terms of mixing. Rather, the variability is most likely due to exposure of the eggshells to the high temperatures of campfires. Despite the variability, eggshells with relatively low A/I values amongst specimens recovered from similar depths (and therefore presumably least influenced by high temperatures) exhibit a gradual increase in A/I with respect to depth, as expected in a stratified deposit. From this observation it is suggested that the identification of heated eggshells will increase confidence in geochronological information provided by A/I. These studies illustrate the complications that arise from campfire-induced acceleration of amino acid racemisation and emphasise that although this phenomenon is common, it is not universally encountered in archaeological contexts.     

CHEMICAL AND MINERALOGICAL ANALYSES OF GALLO-ROMAN WALL PAINTING FROM DIETIKON,SWITZERLAND

Around 90 samples of Roman wall painting dating from the first to the third century AD were analysed using different analytical techniques: X-ray diffraction, X-ray fluorescence, infrared spectrometry, scanning electron microscopy, energy dispersive spectrometry, optical microscopy and physico-chemical tests. The identified pigments are: ash, calcite, carbon black, celadonite, cinnabar, Egyptian Blue, glauconite, goethite, hematite and red lead. Pigment mixtures were used to get other colours such as brown, pink or purple. Three types of plaster were used: a first, and most dominant, with river sand, a second with crushed tile for damp places and a third, to which cinnabar was exclusively applied, was prepared with crushed calcite crystals.     

Source and character of syntaxial hydrothermal calcite veins in Paleoproterozoic crystalline rocks revealed by fine‐scale investigations

Calcite veins in Paleoproterozoic granitoids on the Baltic Shield are the focus of this study. These veins are distinguished by their monomineralic character, unusual thickness and closeness to Neoproterozoic dolerite dykes and therefore have drawn attention. The aim of this study was to define the source of these veins and to unravel their isotopic and chemical nature by carrying out fine‐scale studies. Seven calcite veins covering a depth interval of 50–420 m below the ground surface and composed of breccias or crack‐sealed fillings typically expressing syntaxial growth were sampled and analysed for a variety of physicochemical variables: homogenization temperature (T_h) and salinity of fluid inclusions, and stable isotopes (⁸⁷Sr/⁸⁶Sr, ¹³C/¹²C, ¹⁸O/¹⁶O), trace‐element concentrations (Fe, Mn, Mg, Sr, rare earth elements) and cathodoluminescence (CL) of the solid phase. The fluid‐inclusion data show that the calcites were precipitated mainly from relatively low‐temperature (T_h = 73–106°C) brines (13.4–24.5 wt.% CaCl₂), and the ⁸⁷Sr/⁸⁶Sr is more radiogenic than expected for Rb‐poor minerals precipitated from Neoproterozoic fluids. These features, together with the distribution of δ¹³C and δ¹⁸O values, provide evidence that the calcite veins are not genetic with the nearby Neoproterozoic dolerite dykes, but are of Paleozoic age and were precipitated from warm brines expressing a rather large variability in salinity. Whereas the isotopic and chemical variables express rather constant average values among the individual veins, they vary considerably on fine‐scale across individual veins. This has implications for understanding processes causing calcite‐rich veins to form and capture trace metals in crystalline bedrock settings.