Pore‐scale analysis of trapped immiscible fluid structures and fluid interfacial areas in oil‐wet and water‐wet bead packs

The objective of this study is to obtain quantitative evidence of pore‐scale immiscible fluid distribution in oil‐wet and water‐wet porous media using X‐ray computed microtomography. Temporal and spatial saturation profiles, as well as surface and interfacial areas, are thoroughly analyzed through cycles of drainage and imbibition using samples with different wetting characteristics but similar pore structures. The population of individual immiscible fluid structures (‘blobs’) was also evaluated. The specific nonwetting phase surface areas of both porous media are found to be in close correlation with the specific solid surface area. On the other hand, the differing wetting strengths of the two porous media affect the curvature of the fluid–fluid interface and thus the specific meniscus interfacial area of the two porous media. Although the magnitude of the specific meniscus interfacial areas is different, they both trend toward a maximum at wetting phase saturations of 0.35–0.55. The differences in wetting characteristics are also apparent in the blob populations. The number of blobs in the oil‐wet porous media is three times greater than that of the water‐wet porous media at similar saturations; the increase in population is a result of the increase in the amount of smaller blobs inhabiting the smaller pore spaces. The surface areas of individual blobs as a function of the individual blob volumes are found to closely agree with the specific surface area of a sphere at blob volumes below the minimum individual grain volume and with the specific pore space surface area above this volume. These results show how wettability and saturation history influence the distribution of immiscible fluids within the pore space.     

Pore‐scale investigation on stress‐dependent characteristics of granular packs and the impact of pore deformation on fluid distribution

Understanding the effect of changing stress conditions on multiphase flow in porous media is of fundamental importance for many subsurface activities including enhanced oil recovery, water drawdown from aquifers, soil confinement, and geologic carbon storage. Geomechanical properties of complex porous systems are dynamically linked to flow conditions, but their feedback relationship is often oversimplified due to the difficulty of representing pore‐scale stress deformation and multiphase flow characteristics in high fidelity. In this work, we performed pore‐scale experiments of single‐ and multiphase flow through bead packs at different confining pressure conditions to elucidate compaction‐dependent characteristics of granular packs and their impact on fluid flow. A series of drainage and imbibition cycles were conducted on a water‐wet, soda‐lime glass bead pack under varying confining stress conditions. Simultaneously, X‐ray micro‐CT was used to visualize and quantify the degree of deformation and fluid distribution corresponding with each stress condition and injection cycle. Micro‐CT images were segmented using a gradient‐based method to identify fluids (e.g., oil and water), and solid phase redistribution throughout the different experimental stages. Changes in porosity, tortuosity, and specific surface area were quantified as a function of applied confining pressure. Results demonstrate varying degrees of sensitivity of these properties to confining pressure, which suggests that caution must be taken when considering scalability of these properties for practical modeling purposes. Changes in capillary number with confining pressure are attributed to the increase in pore velocity as a result of pore contraction. However, this increase in pore velocity was found to have a marginal impact on average phase trapping at different confining pressures.     

Pore‐scale multiphase flow experiments in bead packs of variable wettability

The aim of this experimental study is to investigate the impact of wetting characteristics on multiphase flow, sweep efficiency, and residual fluid distribution in unconsolidated porous media. A sequence of oil and water injections was performed on bead packs with uniform porosity and permeability, but different wettability characteristics. Uniform and mixed‐wet bead packs with varying degree of wettability were fabricated to analyze how the residual saturation profiles and the distribution of fluid phases at the pore scale respond to changes in wettability. X‐ray microtomography was used to visualize and analyze the fluid distribution in each bead pack at the end of oil and brine injection. It was found that sweep efficiency was high for the uniform, strongly wetting glass bead pack. For the intermediate‐wet plastic bead pack, we observed evidence of viscous fingering resulting in degenerating sweep efficiency after water injection. In media with mixed wetting surfaces, the spatial distribution of wettability influenced the topology of the saturation profiles and resulted in larger quantities of disconnected fluid blobs. Results also showed that the average blob size was independent of the average residual saturation. In addition, the difference in saturation conditions preceding each injection affected sweep efficiency. The residual saturation after the 1st displacement was higher than the residual saturation after the 2nd displacement.     

Iron precipitation in a natural CO2 reservoir: Jurassic Navajo Sandstone in the northern San Rafael Swell,UT, USA

Diagenetic iron (oxyhydr)oxide minerals are common precipitates expected in CO₂ reservoirs, and these minerals record fluid flow for application to carbon capture and sequestration (CSS). Multiple mineralogy and spectroscopy analyses on a pore to meter scale characterize a well‐exposed, lithologically controlled, iron (oxyhydr)oxides reaction front in the Jurassic Navajo Sandstone. Dolomite is the most prevalent cement (up to 23 area%), followed by only several percent or less of iron (oxyhydr)oxides, kaolinite, illite, and gypsum cements. Bulk geochemistry based on diagenetic mineralogies in the reaction front is compared with the water chemistry from nearby modern spring effluent emanating from the Navajo Sandstone to conclude that similar fluids (i.e., CO₂‐charged, saline waters containing hydrocarbons) are responsible for the precipitation. A second comparison of bulk geochemistry and diagenetic mineralogies of the reaction front with data from other abundant Navajo Sandstone concretions in the Spencer Flat region (in south central Utah) shows that reservoir fluids likely vary spatially and temporally in the porous and permeable Navajo Sandstone. CO₂ injection into porous and permeable, quartz arenite, saline aquifers will likely result in minor clay and abundant dolomite precipitation that will significantly decrease porosity.     

Multiphase flow simulation through porous media with explicitly resolved fractures

Accurate simulation of multiphase flow in fractured porous media remains a challenge. An important problem is the representation of the discontinuous or near discontinuous behaviour of saturation in real geological formations. In the classical continuum approach, a refined mesh is required at the interface between fracture and porous media to capture the steep gradients in saturation and saturation‐dependent transport properties. This dramatically increases the computational load when large numbers of fractures are present in the numerical model. A discontinuous finite element method is reported here to model flow in fractured porous media. The governing multiphase porous media flow equations are solved in the adaptive mesh computational fluid dynamics code IC‐FERST on unstructured meshes. The method is based on a mixed control volume – discontinuous finite element formulation. This is combined with the P_N+1DG‐P_NDG element pair, which has discontinuous (order N+1) representation for velocity and discontinuous (order N) representation for pressure. A number of test cases are used to evaluate the method's ability to model fracture flow. The first is used to verify the performance of the element pair on structured and unstructured meshes of different resolution. Multiphase flow is then modelled in a range of idealised and simple fracture patterns. Solutions with sharp saturation fronts and computational economy in terms of mesh size are illustrated.     

Iron-57 Mössbauer spectral studies of medieval stained glass

⁵⁷Fe Mössbauer spectral data for six excavated and two simulated medieval stained glass samples are reported. Iron-containing precipitates are observed in the two simulated medieval glasses and are responsible for the amber colour of these samples. The ferrous/ferric ratio of the other samples is dependent on the glass composition and glass making conditions. The green glasses are associated with the presence of both ferrous and ferric iron, the ratio being very similar in three of the glasses studied, while in the purple and emerald green glasses the iron which is constitutionally incorporated in the glass is solely in the ferric oxidation state. The UVvisible spectra of some of the glasses are used to assist in interpretation of the colourant action of iron, and the role of Mössbauer spectroscopy in linking separate glass fragments with a common source is also indicated.     

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.     

DIRECT EVIDENCE OF PRIMARY GLASS PRODUCTION IN LATE BRONZE AGE AMARNA,EGYPT

This paper presents direct archaeological evidence for the primary production of glass at the LBA site of Tell el‐Amarna, in the form of numerous finds of semi‐finished glass. The diagnostic microstructural and chemical composition of these finds is presented alongside macroscopically similar finds, of shapeless lumps of finished white glass. The semi‐finished glass was found to contain numerous inclusions of residual quartz and newly formed lime‐rich crystal phases, but no added colorant. However, several samples of semi‐finished glass have antimony oxide levels comparable to those of finished white glass, suggesting that the opacifier was added to the initial glass‐making batch. The results are discussed in comparison with the evidence for glass‐making from Qantir – Pi‐Ramesse, identifying some close technical similarities, which indicate that the same technological processes were used at both sites for the production of glass.     

Cementation and the hydromechanical behavior of siliciclastic aquifers and reservoirs

Progressive cementation and lithification significantly influence the mechanical and hydrologic properties of granular porous media through elastic stiffening and permeability reduction. We use published data that quantify the effect of grain‐bridging cement distribution in granular porous media at the grain scale to investigate the influence of variable cement content on the competing roles of hydrologic and mechanical effects on fluid flow and deformation at the reservoir scale. The impact of quartz overgrowths in natural samples was quantified using a bond‐to‐grain ratio, allowing a geologically meaningful interpretation of percent cement in conceptual models of quartz cementation. An increase in the bond‐to‐grain ratio from 1 to 2.2 (~1–15% cement by volume) results in a 1.4‐fold increase in Young's modulus and an ~1000‐fold decrease in permeability. The hydromechanical properties of a suite of variably cemented natural samples are used as input into two‐dimensional, kilometre‐scale, axially symmetric poroelastic models of an isotropic confined aquifer. Models isolating the hydrologic and mechanical effects of cementation indicate that the hydrologic properties dominate the overall mechanical response, controlling both the volume and magnitude of deformation. Incorporation of changes in hydrologic properties due to cementation is therefore essential to capturing the first‐order physics of coupled aquifer behavior.     

Morphological evolution of three‐dimensional chemical dissolution front in fluid‐saturated porous media: a numerical simulation approach

This paper is concerned with the morphological evolution of three‐dimensional chemical dissolution fronts that occur in fluid‐saturated porous media. A fully coupled system between porosity, pore‐fluid flow and reactive chemical species transport is considered to describe this phenomenon. Using the newly presented concept of the generalized dimensionless pore fluid pressure‐gradient, which can be used to represent the interaction between solute advection, solute diffusion, chemical kinetics and the shape factor of the soluble mineral, a theoretical criterion has been established to assess the likelihood of instability at a chemical dissolution front in the reactive transport system. To simulate the chemical dissolution front evolution in a three‐dimensional fluid‐saturated porous medium, a numerical procedure combining both the finite difference method and the finite element method has been proposed. As the problem belongs to a complex system science problem, a small randomly generated perturbation of porosity is added to the initial porosity of a three‐dimensional homogeneous domain to trigger instability of a planar chemical dissolution front during its propagation within the fluid‐saturated porous medium. To test the correctness and accuracy of the proposed numerical procedure, a three‐dimensional benchmark problem has been constructed and the related analytical solution has been derived. This enables using the proposed numerical procedure for simulating the morphological evolution of a three‐dimensional chemical dissolution front from a stable, planar state into an unstable, fingering state. The related numerical results demonstrate that the proposed numerical procedure is useful for, and capable of, simulating the morphological instability of a three‐dimensional chemical dissolution front within a fluid‐saturated porous medium.     

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.     

ANTIMONATE OPAQUE GLAZE COLOURS FROM THE FAIENCE MANUFACTURE OF LE BOIS D’ÉPENSE (19TH CENTURY,NORTHEASTERN FRANCE)*

Three types of antimony‐based, opaque ceramic colours were used in the faience workshop of Le Bois d’Épense during the first decades of the 19th century; that is, yellow, tawny and green. Yellow is generated by lead antimonate crystals (Naples Yellow), which are incorporated into an uncoloured glass matrix. According to SEM–EDS measurements, these pigments contain iron. The tawny colour is the optical result of the combined presence of similar yellow, iron‐bearing lead antimonate particles in a Fe‐rich, brownish glass matrix. The green opaque colour is produced by the combination of a blue cobalt glass and yellow Pb–Sn–Fe‐antimonate crystals. Cores of zoned pigments lighten the recipes, according to which the pigments were produced. First, they were synthesized by calcination, ground and then mixed with a colourless, brown or blue glass powder. The resulting powder mixture was added to a liquid agent and used as high‐temperature ceramic colour.     

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

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

The relationship between enamelling on ceramics and on glass in the Islamic world

In a recent paper, Mason et al. (2001) demonstrated that enamels on mina’i ware, a Persian ceramic of the 12th century, were applied using a special firing of short duration. A similar principle was exploited to enamel glass, beginning in Syria in about the same period. This gives new credence to the long‐standing idea that the origin of enamelling on glass resulted in part from an interaction between glass workers and potters.     

MATERIAL CHARACTERIZATION OF CERAMIC TILE MOSAIC FROM TWO 17TH‐CENTURY ISLAMIC MONUMENTS IN NORTHERN INDIA

Coloured tiles from two northern Indian monuments were analysed for their body and glaze composition. The results suggest that three different groups of tiles were used, all comprising a stonepaste body with alkali glaze. One group has strong similarities to a major Indian glass group, known as high alumina mineral natron glass, while the other two are similar to Western and Central Asian plant ash glazes, although with much lower lime content. The colorants conform with those usually employed in pre‐modern glazes, with lead‐tin yellow Type I and Type II for opaque yellow, copper blue‐turquoise, cobalt blue, manganese purple, and green through mixing of lead‐tin yellow and copper blue.     

Glass beads and pendants from Meroitic and Nobadian Lower Nubia,Sudan: Chemical compositional analysis using laser ablation‐inductively coupled plasma‐mass spectrometry

This paper presents a detailed elemental analysis of 64 glass beads and pendants dated to the Meroitic period (first–third centuries ad ) and the Nobadian period (fourth–sixth centuries) from burial sites in the Lower Nubian Nile Valley region. Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) was used to determine the chemical composition of the glass and to gain knowledge about its origin. Four main glass types were identified: low‐alumina soda‐lime glass, high‐alumina glass, plant‐ash soda‐lime glass, and mixed‐alkali glass. Mineral soda‐lime glass (m‐Na‐Ca) of East Mediterranean/Egyptian provenance is dominant within the low‐alumina glass group from Meroitic and Nobadian periods. Mineral soda high‐alumina glass (m‐Na‐Al) appeared in the Nobadian bead assemblages, and the m‐Na‐Al 1 subtype was produced in Sri Lanka/South India. An initial insight into the origin of the glass beads in Nubia from the first to sixth centuries is described, indicating the first evidence for the presence of Asian objects in Nubia. The data obtained for the bead trade in North‐east Africa in this study has allowed a new light to be shed on the westward flow of Asian glass during a time of intensive maritime trade contacts with the wider Indian Ocean world.     

ARCHAEOLOGICAL VOLCANIC GLASS FROM THE SITE OF ROCCHICELLA (SICILY,ITALY)*

The site of Rocchicella, near Catania, in eastern Sicily, has yielded important archaeological evidence from prehistoric times to the Middle Ages. Extensive archaeological investigations of cultural layers dating from the Palaeo‐Mesolithic to the Copper Age have recently been undertaken, and volcanic glass, mainly obsidian, has been collected in the course of excavation. To determine the provenance of this volcanic glass, a non‐destructive elemental analysis was carried out to measure the concentration of characteristic trace elements. The analysis was carried out using a new XRF spectrometer equipped with a beam stability controller and a quantitative method developed at the LANDIS laboratory of the INFN–CNR Institutes of Catania. In addition to the obsidian, it was demonstrated for the first time that a local vitreous material similar to obsidian, but displaying a completely different composition, was used during all the investigated periods. This material was identified as a basaltic glass, characterized by a superficial product of devitrification called palagonite. Analysis of the obsidians has led to the identification of the island of Lipari as the provenance source. High‐ and low‐power microscopic use‐wear analysis on obsidian and basaltic glass artefacts indicated that soft wood and plant matter might have been processed at the site.     

ANALYSIS OF LATE BRONZE AGE GLASS AXES FROM NIPPUR—A NEW COBALT COLOURANT

A multidisciplinary study of a unique group of Late Bronze Age (LBA) ceremonial glass axe heads and other artefacts shows that these are the first significant group of glasses coloured with cobalt to be identified from the Near East. The axes were excavated from the site of Nippur, in present‐day Iraq. Several are incised with the names of three kings, which dates the material to the 14th–13th centuries bc . Analysis by laser ablation inductively coupled plasma mass spectrometry (LA–ICPMS) indicates that the glass had high magnesia (MgO) and potash (K₂O) associated with a plant‐ash flux and was coloured blue by copper or a combination of copper and cobalt. These glasses are similar, but not identical, in major element composition to blue‐coloured glasses manufactured in ancient Egypt and elsewhere in Mesopotamia in the same period. However, the Nippur cobalt‐ and copper‐coloured glasses exhibit significantly different trace elemental compositions compared to Egyptian glass coloured with cobalt, showing that the ancient Near Eastern glassmakers had clearly identified and utilized a distinctive cobalt ore source for the colouring of this glass. Since it was previously thought that the only cobalt ores exploited in the LBA were exclusively of Egyptian origin, this new finding provides new insights on the origins of glass and how it was traded during the Bronze Age period.     

The Production and Circulation of Carthaginian Glass Under the Rule of the Romans and the Vandals (Fourth to Sixth Century ad): A Chemical Investigation

Fifty‐seven glass samples from Carthage dating to the fourth to sixth century ad were analysed using the electron microprobe. The results show that these samples are all soda–lime–silica glass. Their MgO and K₂O values, which are below 1.5%, suggest that they were made from natron, a flux that was widely used during the Roman period. The major and minor elements show that these samples can be divided into four groups, three of which correspond to the late Roman period glass groups that were found throughout the Roman Empire: Levantine I, and ‘weak’ and ‘strong’ HIMT. Of particular interest is our Group 2, which is technologically and compositionally similar to HIMT glass and the CaO and Al₂O₃ values of which are similar to those of Levantine I. Glass of similar composition has been reported by several authors and is predominantly found dating from the late fifth to seventh century. This could represent a ‘new’ glass group; therefore further study is needed to determine its origin. Also, this study suggests that the Vandal invasion in North Africa did not disrupt the glass trade between Carthage and the Levantine coast.     

Analysis of Medieval and Post‐Medieval Glass Fragments from the Dubrovnik Region (Croatia)

Dubrovnik was an important trade city throughout the medieval and post‐medieval time period, maintaining its own glass production from the 14th to the 16th century. Unfortunately, Dubrovnik glass discoveries have not been well investigated up until now, except via archival data in large data analyses. In the following work, we will shed new light on the glass material found in this region, which has diverse origins, chronology, typology and style. Medieval and post‐medieval glass finds (10th/12th–18th centuries) discovered during archaeological excavations in Dubrovnik and the Dubrovnik region were analysed using particle‐induced X‐ray emission (PIXE) and particle‐induced gamma‐ray emission (PIGE), which revealed three main compositional groups: natron glass, plant‐ash glass and potash glass. This demonstrates the important commercial links present between Dubrovnik and other major glass‐making centres.