EVALUATION OF BINDER/AGGREGATE RATIOS IN ARCHAEOLOGICAL LIME MORTARS WITH CARBONATE AGGREGATE: A COMPARATIVE ASSESSMENT OF CHEMICAL,MECHANICAL AND MICROSCOPIC APPROACHES*

This paper reports on the comparative evaluation of traditional and innovative methods for the investigation of mortar technology. Preliminary results of various approaches to determining the mix proportions in lime mortars with carbonate aggregate are presented. Quantitative analysis was tested on ad hoc prepared mortars of known composition containing carbonate aggregates of different origin (travertine and Bath limestone). Wet chemical methods, manual disaggregation and Digital Image Analysis of thin sections and cross‐sections stained with Alizarin Red S were tested. The advantages and drawbacks of the different approaches are discussed, and applications to the analysis of archaeological mortars and plasters are highlighted.     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

Differentiating between anthropogenic calcite in plaster,ash and natural calcite using infrared spectroscopy: implications in archaeology

Infrared spectroscopy provides information not only on the type of calcium carbonate polymorph, but also on the extent of atomic order. In calcite, three major infrared absorption peaks are identified: ν₃, ν₂, and ν₄. It was shown that the ratio between ν₂ and ν₄ bands reflects the order of the calcite crystal structure. In this paper we analyse this ratio in geologically formed calcites, archaeological plasters, modern plasters and experimentally prepared plasters. For the geological calcite, the values of the ν₂/ν₄ ratio are around 3, whereas for the experimentally prepared plasters, the values are around 6.5. The ν₂/ν₄ ratio for archaeological plasters varies from 3 to 6. This shows that a high ratio is indicative of disorder in the crystal, and implies that the calcite was formed from calcium oxide at high temperatures. It also implies that this disorder can be preserved for at least 14,000 years. The ν₂/ν₄ ratio of calcite from archaeological sites can thus be used to differentiate between anthropogenic calcite, such as in plaster, mortar and wood ash, from geogenic calcite, such as in limestone. The ratio may also be used to identify plaster or ash that still retains its original crystals and therefore carbon-14 content.     

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.     

Permeability of the Mercia Mudstone: suitability as caprock to carbon capture and storage sites

The Upper Triassic Mercia Mudstone is the caprock to potential carbon capture and storage (CCS) sites in porous and permeable Lower Triassic Sherwood Sandstone reservoirs and aquifers in the UK (primarily offshore). This study presents direct measurements of vertical (k_v) and horizontal (k_h) permeability of core samples from the Mercia Mudstone across a range of effective stress conditions to test their caprock quality and to assess how they will respond to changing effective stress conditions that may occur during CO₂ injection and storage. The Mercia samples analysed were either clay‐rich (muddy) siltstones or relatively clean siltstones cemented by carbonate and gypsum. Porosity is fairly uniform (between 7.4 and 10.7%). Porosity is low either due to abundant depositional illite or abundant diagenetic carbonate and gypsum cements. Permeability values are as low as 10^?20 m² (10nD), and therefore, the Mercia has high sealing capacity. These rocks have similar horizontal and vertical permeabilities with the highest k_h/k_v ratio of 2.03 but an upscaled k_h/k_v ratio is 39, using the arithmetic mean of k_h and the harmonic mean of k_v. Permeability is inversely related to the illite clay content; the most clay‐rich (illite‐rich) samples represent very good caprock quality; the cleaner Mercia Mudstone samples, with pore‐filling carbonate and gypsum cements, represent fair to good caprock quality. Pressure sensitivity of permeability increases with increasing clay mineral content. As pore pressure increases during CO₂ injection, the permeability of the most clay‐rich rocks will increase more than carbonate‐ and gypsum‐rich rocks, thus decreasing permeability heterogeneity. The best quality Mercia Mudstone caprock is probably not geochemically sensitive to CO₂ injection as illite, the cause of the lowest permeability, is relatively stable in the presence of CO₂–water mixtures.     

RADIOCARBON DATING OF MORTARS FROM ANCIENT GREEK PALACES

This study deals with radiocarbon dating of lime mortars which were used as supports for Mycenaean and Minoan paintings. The ¹⁴C dates are. on the whole, compatible with the historical data. and thus show that a large proportion of the Mycenaean surficial coatings can be dated by the radiocarbon method. However. in order to determine the age of the mortars accurately. it is necessary to evaluate the amount of sedimentary carbonate which may have been added to them. It is shown here that the oxygen and carbon isotope compositions of lime mortars are significant indicators that such a mixing actually took place.     

The ancient pozzolanic mortars and concretes of <Emphasis Type="Italic">Heliocaminus</Emphasis> baths in Hadrian’s Villa (Tivoli,Italy)

The aim of this work is the physical and mineralogical-petrographic characterization of the mortars from the Baths with Heliocaminus, a special and unique architectural building in the complex of the Hadrian’s Villa in Tivoli. Thirty samples were investigated for composition and physical properties (density, porosity, water absorption, mechanical strength, particle size distribution of aggregate, etc.), representative of eight mortar groups: cubilia bedding mortar, brick bedding mortars, floor-coating and wall-coating bedding mortars, floor (rudus) and wall conglomerates (trullisatio), vault concretes, and lime plasters (arriccio). Physical parameters, together with the microscopic analysis and binder/aggregate ratio determined in three ways using image analysis (on thin sections and on specimens) and weight-data from dissolution of binder, have shown an interesting relationship between the physical-compositional characteristics and the function of mortars within the structure of the Heliocaminus baths. To identify the minerals and the reactant phases between binder and aggregate, as well as the hydraulic degree, selected samples were analyzed with x-ray powder diffraction, thermogravimetry, and differential scanning calorimetry techniques. The obtained results provide a close relation between pozzolanic characteristics and physical-mechanical properties of the mortars (i.e., punching strength index).     

Evidence of physico–chemical and isotopic modifications in archaeological bones during controlled acid etching

It has been repeatedly shown that palaeoecological inferences from the elemental and isotopic content of carbonate hydroxylapatite of fossil teeth and bones are unrecoverable without removing diagenetic overprinting by chemical pretreatments. Such pretreatments may in turn cause modification of the biogenic signature. In this paper, we focus upon optimal removal of Ca–bearing carbonates (mainly calcite). In order to control the progress with time of calcite dissolution, we perform leaching under vacuum, and we monitor the evolution of the pH, pCO₂, δ¹³C of released CO₂, %C, δ¹³C and δ¹⁸O of the remaining mineral. For a set of different Quaternary bones and teeth, mass and isotopic balances indicate that 1 hour at most is necessary for complete dissolution of calcite with an optimal conservation of carbonate hydroxylapatite. Long–lasting experiments lead to a fractionation of hydroxylapatite ¹⁸O/¹⁶O carbonates.     

Fluid inclusion and isotopic constraints on the origin of ore‐forming fluid of the Jinman–Liancheng vein Cu deposit in the Lanping Basin,western Yunnan,China

Extensive quartz–carbonate–Cu sulfide veins occur in clastic rocks and are spatially related to Paleocene granites in the western border of the Lanping Basin, western Yunnan, China. Abundant aqueous‐carbonic fluid inclusions occur in these veins but their origin is debated. In the Jinman–Liancheng deposit, individual primary inclusion groups contain either exclusively liquid‐rich inclusions (Gl), or coexisting liquid‐rich and vapor‐rich inclusions (Glv). Microthermometry and estimate of CO₂ content indicate that type Gl inclusions either have homogenization temperatures (Th) 238–263°C and contain c. 3.9–5.5 mole % CO₂, or have Th 178–222°C and contain c. 1.6–3.2 mole % CO₂. Type Glv inclusions are thought to represent samples of fluid unmixing that occurred at 183–218°C. At that time, the liquid phase in the unmixing fluid may contain c. 2.0–3.3 mole % CO₂. As such, the correlation of CO₂ content with Th for type Gl inclusions is thought to be caused by fluid unmixing with decreasing temperature and subsequent CO₂ escape. δ¹⁸O and δD values of the parent water mainly fall in the field below that of primary magmatic water, indicative of fluid derivation from degassed (in open system) magmatic water, with no contributions from basinal or meteoric water. Initial Sr isotopic compositions of hydrothermal carbonates suggest that the fluid was magmatic, probably derived from the Paleogene granites. δ¹³C_PDB values (?4‰ to ?7‰) of the hydrothermal carbonates and δ³⁴S_V‐CDT values of sulfides (mainly ?11‰ to +5‰) indicate that the carbon and sulfur can be derived from (degassed) magma and/or nonmagmatic sources. The CO₂‐rich and magmatic‐water‐derived fluid at Jinman–Liancheng differs from the CO₂‐poor and basinally derived fluid in sediment‐hosted stratiform Cu (SSC) deposits, which suggests that there are no genetic linkages between the vein Cu and SSC deposits in the Lanping Basin.     

PIGMENTS AND PLASTERS FROM THE ROMAN SETTLEMENT OF THAMUSIDA (RABAT,MOROCCO)

A total of 22 samples were taken both from plasters still in situ and from collapsed material recovered by French, Italian and Moroccan teams at the Roman settlement of Thamusida (Rabat, Morocco). The sample characterization was obtained using optical microscopy, scanning electron microscopy, image analysis and Raman micro‐spectroscopy. Plaster aggregate was made using a mixture of sands and clays that outcrop nearby, while lime was probably produced using the local limestone crust, as was further verified for the mortars. The plasters from the bath complexes (public buildings) and the Temple à trois cellae (sacred building) were very poorly made, while those from areas VII and XX (private buildings) indicated the involvement of more expert masons. The pigments used were cinnabar, red ochre, yellow ochre, Egyptian blue, green earth, chalk white and carbon black. The overall manufacture was of low quality, and hence perfectly comparable to that observed in other Roman Provinces. With respect to Italy and to other Mediterranean Roman sites, Thamusida fits well within an aesthetic and technical koinè that differentiates sites of the Italian peninsula from those in the Provinces.     

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.     

The effect of deformation on permeability development in anhydrite and implications for caprock integrity during geological storage of CO2

Geological storage of CO₂ in depleted oil and gas reservoirs is one of the most promising options to reduce atmospheric CO₂ concentrations. Of great importance to CO₂ mitigation strategies is maintaining caprock integrity. Worldwide many current injection sites and potential storage sites are overlain by anhydrite‐bearing seal formations. However, little is known about the magnitude of the permeability change accompanying dilatation and failure of anhydrite under reservoir conditions. To this extent, we have performed triaxial compression experiments together with argon gas permeability measurements on Zechstein anhydrite, which caps many potential CO₂ storage sites in the Netherlands. Our experiments were performed at room temperature at confining pressures of 3.5–25 MPa. We observed a transition from brittle to semi‐brittle behaviour over the experimental range, and peak strength could be described by a Mogi‐type failure envelope. Dynamic permeability measurements showed a change from ‘impermeable’ (<10^?21 m²) to permeable (10^?16 to 10^?19 m²) as a result of mechanical damage. The onset of measurable permeability was associated with an increase in the rate of dilatation at low pressures (3.5–5 MPa), and with the turning point from compaction to dilatation in the volumetric versus axial strain curve at higher pressures (10–25 MPa). Sample permeability was largely controlled by the permeability of the shear faults developed. Static, postfailure permeability decreased with increasing effective mean stress. Our results demonstrated that caprock integrity will not be compromised by mechanical damage and permeability development. Geofluids (2010) 10 , 369–387     

Mortars in context: An integrated study of mortars and plasters from the so-called Ginnasio in Solunto (Sicily,Italy)

This paper presents a multipronged scientific study of mortars and plasters of the so-called Ginnasio in the Hellenistic–Roman city of Solunto (Sicily, Italy). A selection of 16 well-contextualized samples was collected to represent different functions and building phases of this private house. The results show that a variety of locally available raw materials was used as aggregates and to produce binders. The diversity of raw materials’ sources and production techniques identified in this study reveals the advanced technological knowledge of the builders of Solunto, indicating a complex relationship between the settlement's cityscape and its surrounding landscape.     

INVESTIGATION OF ELECTRON PARAMAGNETIC RESONANCE PEAKS IN SOME POWDERED GREEK WHITE MARBLES*

Within the context of white marble provenance research, 42 powdered white Greek marbles have been characterized using electron paramagnetic resonance (EPR) spectroscopy. Phase analysis was first carried out to separate calcitic and dolomitic marbles, then EPR spectra of Mnuc were studied. Investigation of other marble EPR spectra, especially around g — 2.00, led us to characterize five different signals. The intensities of Mn²⁺ lines permit the separatum of eight quarries into two groups, allowing a first discrimination, in the g = 2,00 region, only one signal has been found to be useful for provenance research objectives. The results are cheering and should lead to many other similar experiments.     

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.     

Method-dependent variations in stable isotope results for structural carbonate in bone bioapatite

Stable carbon and oxygen isotope values (δ¹³C, δ¹⁸O) were obtained for structural carbonate in the bioapatite of archaeological bones from Guatemala and Sudan using several common analytical methods. For the Sudan samples, the different methods produced δ¹³C values within ±0.1‰ and δ¹⁸O values within ±0.7‰, on average. The isotopic results for the Guatemala samples were similar in reproducibility to the Sudan samples when obtained using methods that employed lower reaction temperatures and reactions in sealed vessels. However, many Guatemala samples had highly variable and extremely low δ¹⁸O values when reacted at higher temperatures in vessels that remained open to cryogenic traps. The latter arrangement caused reaction products to be removed immediately upon their production. The anomalously low δ¹⁸O values are related to the production of a contaminant gas that causes the m/z 46/44 ratio to be lowered, either by adding to the m/z 44 peak or subtracting from the m/z 46 peak. That said, potential contaminant materials were not detectable in “anomalous” bones using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, or inductively-coupled plasma atomic emission spectroscopy. However, subtle structural and chemical differences between “normal” and “anomalous” samples were observed, most notably in the FTIR ν₂ CO₃ domain. We suggest that these changes promote volatilization of an oxyphosphorus compound and oxygen isotope fractionation between PO⁻ derived from this compound and CO₂ derived from bone carbonate. Production of the contaminant gas and the related “anomalous” δ¹⁸O values is reversible if the reaction occurs within a sealed vessel for a sufficient period of time, which allows a “back-reaction” to occur.     

Thermally assisted OSL: A potent tool for improvement in minimum detectable dose and extension of dose range of Al2O3:C

The influence of electron-phonon interaction on the shape of the optically stimulated luminescence decay curve of Al₂O₃:C has been studied using thermally assisted optically stimulated luminescence (TA-OSL). The minimum detectable dose (MDD) of a phosphor depends on the standard deviation of the background signal which affects the signal-to-noise ratio. The standard deviation of the background signal reduces at lower stimulation light intensity while the readout time increases. Further, measurement at higher temperature enhances the OSL signal with faster decay due to the temperature dependence of photo-ionization cross-section. To achieve the same decay constant and more signal, the temperature of measurement was raised. As a result of lowering the stimulation in-tensity at higher temperature (85°C) the overall MDD of α-Al₂O₃:C was found to improve by 1.8 times. For extension of dose linearity in higher range, deeper traps were studied by simultaneous application of CW-OSL and thermal stimulation up to 400°C, using a linear heating rate of 4K/s. By using this method, two well defined peaks at 121°C and 232°C were observed. These TA-OSL peaks have been correlated with two deeper defects which can be thermally bleached at 650°C and 900°C respectively. These deeper defects are stable up to 500°C, so they can store absorbed dose information even if the sample is inadvertently exposed to light or heat. The dose vs. TA-OSL response from deep traps of α-Al₂O₃:C was found to be linear up to 10 kGy, thus extending its application for high dose dosimetry.     

Simulation of the impact of faults on CO2 injection into sandstone reservoirs

Numerical simulations of multiphase CO₂ behavior within faulted sandstone reservoirs examine the impact of fractures and faults on CO₂ migration in potential subsurface injection systems. In southeastern Utah, some natural CO₂ reservoirs are breached and CO₂‐charged water flows to the surface along permeable damage zones adjacent to faults; in other sites, faulted sandstones form barriers to flow and large CO₂‐filled reservoirs result. These end‐members serve as the guides for our modeling, both at sites where nature offers ‘successful’ storage and at sites where leakage has occurred. We consider two end‐member fault types: low‐permeability faults dominated by deformation‐band networks and high‐permeability faults dominated by fracture networks in damage zones adjacent to clay‐rich gouge. Equivalent permeability (k) values for the fault zones can range from <10^?14 m² for deformation‐band‐dominated faults to >10^?12 m² for fracture‐dominated faults regardless of the permeability of unfaulted sandstone. Water–CO₂ fluid‐flow simulations model the injection of CO₂ into high‐k sandstone (5 × 10^?13 m²) with low‐k (5 × 10^?17 m²) or high‐k (5 × 10^?12 m²) fault zones that correspond to deformation‐band‐ or fracture‐dominated faults, respectively. After 500 days, CO₂ rises to produce an inverted cone of free and dissolved CO₂ that spreads laterally away from the injection well. Free CO₂ fills no more than 41% of the pore space behind the advancing CO₂ front, where dissolved CO₂ is at or near geochemical saturation. The low‐k fault zone exerts the greatest impact on the shape of the advancing CO₂ front and restricts the bulk of the dissolved and free CO₂ to the region upstream of the fault barrier. In the high‐k aquifer, the high‐k fault zone exerts a small influence on the shape of the advancing CO₂ front. We also model stacked reservoir seal pairs, and the fracture‐dominated fault acts as a vertical bypass, allowing upward movement of CO₂ into overlying strata. High‐permeability fault zones are important pathways for CO₂ to bypass unfaulted sandstone, which leads to reduce sequestration efficiency. Aquifer compartmentalization by low‐permeability fault barriers leads to improved storativity because the barriers restrict lateral CO₂ migration and maximize the volume and pressure of CO₂ that might be emplaced in each fault‐bound compartment. As much as a 3.5‐MPa pressure increase may develop in the injected reservoir in this model domain, which under certain conditions may lead to pressures close to the fracture pressure of the top seal.     

Constraints on the precision of SAR in equivalent dose estimations close to saturation in quartz

Difficulties in evaluating accurate equivalent doses for Late Quaternary sediments from the south coasts of Greece arose in the course of SAR measurements. Large scatter among apparent equivalent doses perplexed the evaluation of accurate mean estimates in circumstances where very large doses were involved. Besides, dose recovery experiments revealed that when intersection of the natural signal occurs onto the saturating segment of the growth curve, a distinct relationship between D_e and growth curve shape occurs. At very low slope angles, SAR tends to overestimate the recovered dose. The mechanism which controls the spread in equivalent dose estimation is investigated.     

Characterization of Late Prehistoric Plasters and Mortars from Erimi – Laonin tou Porakou (Limassol,Cyprus)

Several plasters and mortars from the Middle Bronze Age site of Erimi – Laonin tou Porakou (Cyprus) were analysed in order to perform a technological characterization. Morphological (SEM), elemental (EDX), mineralogical (XRPD), petrographic (polarized OM, SEM–EDX), thermal (TGA) and spectroscopic (FT–IR) techniques were applied. Plasters and mortars were identified as pyrotechnological lime products, obtained using local raw materials and containing a moderate amount of spathic calcite fragments. The use of organic fibres was ascertained and a seminal use of a crumbled ceramic as additive was evidenced.