Altered Layer Research Articles

First evidence for Neoproterozoic rocks offshore South-East Greenland

AbstractMeta-sedimentary rocks recovered beneath Palaeogene basalts near the base of Ocean Drilling Program (ODP) Leg 152-917A offshore South-East Greenland were thought to be of Late Cretaceous age. This interpretation, however, has several inconsistencies as it requires a tectono-metamorphic event during the Cretaceous not recognized in the North Atlantic region, and the presence of a wide Mesozoic sedimentary basin that extended from SE-Greenland to the Rockall Plateau, for which there is currently no evidence. Here, we report a Neoproterozoic U/Pb apatite age of 905 ± 21 Ma and a younger 40Ar/39Ar isochron whole-rock age of 820 ± 40 Ma for an altered tuff layer that occurs in the upper part of the meta-volcaniclastic sequence recovered from hole 917A. The 40Ar/39Ar step-heating ages on biotite and whole-rock mini-cores from deeper in hole 917A yielded Palaeoproterozic dates that cluster around 1950 to 1850 Ma, pointing toward a Palaeoproterozoic source. The U/Pb apatite date is interpreted as the eruption age of the tuff layer, whereas the younger whole-rock 40Ar/39Ar age is consistent with low-temperature greenschist alteration of volcanic glass and secondary mineral growth during sedimentary burial in an extensional regime. The c. 905 Ma age for the tuff provides the first evidence for Neoproterozoic rocks offshore South-East Greenland and suggests a correlation between this sequence and the Torridon Group in the Hebridean Foreland of the Scottish Caledonides. The calc-alkaline nature of the volcaniclastic rocks and the age of the tuff layer point toward a source area with arc-magmatism related to the Renlandian event of the Valhalla Orogeny.

Chemical durability and degradation mechanisms of CsPbI3 as a potential host phase for cesium and iodine sequestration.

Effective nuclear waste management of radioactive cesium and off-gas iodine from complex waste streams of used fuels is essential for the sustainable development of advanced nuclear fuel cycles. Once cesium and iodine are separated from their respective waste streams, host phases are required to immobilize them into a durable waste form matrix for long-term disposition. The inorganic metal halide perovskite, CsPbI3, has a unique crystal structure capable of incorporating both cesium and iodine simultaneously. Exposure to groundwater in geological repositories is a long-term concern for waste forms, as this may cause corrosion and decrease the waste form's ability to retain radionuclides. In this study, we explore the potential of CsPbI3 perovskite as a promising host phase to incorporate Cs and I, and investigate its chemical durability and degradation mechanisms in an aqueous environment. CsPbI3 was synthesized through a solution-based method and was consolidated into dense pellets by spark plasma sintering. The chemical durability of the CsPbI3 pellets was evaluated by static leaching tests in deionized water at different temperatures of 25, 58, and 90 °C. The elemental release mechanisms and surface alteration of the monolithic CsPbI3 pellets were investigated. Both I and Cs displayed a non-congruent leaching behavior and faster release rates as compared to Pb, particularly at longer leaching durations and higher temperatures. At the initial leaching stage, a PbI2 alteration layer formed on the surface of the pellet due to the rapid release of Cs and I, followed by the formation of a PbI(OH) alteration layer. The activation energies for both dissolution and diffusion controlled mechanisms were determined to be 44.90 kJ mol−1 and 45.40 kJ mol−1 for Pb, 27.10 kJ mol−1 and 40.82 kJ mol−1 for I and 24.27 kJ mol−1 and 23.86 kJ mol−1 for Cs, respectively. These results show a clear decrease in activation energies from Pb to I and Cs, suggesting a preferential release of I and Cs. The solution-based synthesis of CsPbI3 as a host phase for Cs and I and the fundamental understanding of the chemical durability and degradation behavior will be useful for further exploring its application for immobilizing iodine and cesium into final durable waste forms for long-term geological disposition.

Machining subsurface deformation under various rake angles

Subsurface plastic deformation has attracted a great deal of attention due to its tight relation with surface hardening, microstructure alteration, grain refinement, and white layer formation. Therefore, it is critical to study the subsurface plastic deformation during the machining process. In this study, the digital image correlation technique (DIC) is used to measure the subsurface deformation during the orthogonal cutting process. The cutting tool’s rake angle is varied by a specially designed experimental setup. FEM simulations are carried out to predict the subsurface deformation and comparisons with the experimental measurements are conducted. This study can deepen the understanding of the generation of surface integrity and can be further developed for implementation into the online conditioning of surface integrity.

Hybrid Fuzzy-Analytic Hierarchy Process (AHP) Model for Porphyry Copper Prospecting in Simorgh Area, Eastern Lut Block of Iran

The eastern Lut block of Iran has a high potential for porphyry copper mineralization due to the subduction tectonic regime. It is located in an inaccessible region and has harsh arid conditions for traditional mineral exploration campaigns. The objective of this study is to use Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) remote sensing data for porphyry copper exploration in Simorgh Area, eastern Lut block of Iran. Hydrothermal alteration zones such as argillic, phyllic and propylitic zones associated with porphyry copper systems in the study were identified using false color composition (FCC), band ratio (BR), principal component analysis (PCA) and minimal noise fraction (MNF). The thematic alteration layers extracted from FCC, BR, PCA and MNF were integrated using hybrid Fuzzy-AHP model to generate a porphyry copper potential map for the study area. Four high potential zones were identified in the central, western, eastern and northeastern of the study area. Fieldwork was used to validate the approach used in this study. This investigation exhibits that the use of hybrid Fuzzy-AHP model for the identification of hydrothermal alteration zones associated with porphyry copper systems that is typically applicable to ASTER data and can be used for porphyry copper potential mapping in many analogous metallogenic provinces.

On the dissolution of a borosilicate glass with the use of isotopic tracing – Insights into the mechanism for the long-term dissolution rate

An understanding of the mechanisms responsible for controlling the long-term corrosion rate of nuclear waste glass is paramount if reliable glass dissolution models are to be used to calculate the controlled release of radionuclides from nuclear waste glass under geologic disposal conditions. Understanding the mechanism that controls silicate glass dissolution rates is also important for natural glasses to understand the role from the dissolution of these glasses has on the composition of natural aquatic systems. Two general mechanisms appear to be responsible for the elemental release from glass to the surrounding biosphere – ion exchange (release principally of alkalis) and matrix dissolution (release of the structural components of the glass). Key unknowns related to these mechanisms are the impact of surface layers on the altered glass and how these layers participate in corrosion. To better understand the impact of these layers on the long-term glass corrosion rate, we made two glasses of the same elemental composition, but with selected elements enriched in specific isotopes for B (11B), Li (6Li), and Si (29Si). We reacted these glasses for 1 y then the solutions from each were exchanged and the chemistry of the solutions and the solids were followed for another 2 y (a total of 3 y). This allowed us to follow changes in the glasses with respect to these elements and how these elements were transported through the alteration layers with time and, for at least one element, into the glass and to deconvolute some competing kinetic steps, such as matrix dissolution and ion exchange. Results from these experiments demonstrate that the release behavior of different elements is strongly dependent on their structural role in the glass (e.g. network formers and modifiers), but, more importantly, the role of water transport and subsequent ion exchange has in the long-term dissolution of the glass studied here. In this article, we highlight the behavior of four elements: lithium, sodium, silicon, and boron. Lithium and sodium, network modifying elements, have similar chemistries. The behavior of Li could be tracked in more detail by following both 6Li and 7Li; Li penetrates through the gel layer in both directions without hinderance and is released from the glass deeper than Na. Silicon, a network forming element, reacts with the silica-rich alteration layer. Boron, a network forming element, does not accumulate in the gel or the pristine glass and has a very sharp elemental profile between the pristine glass and alteration layer. Boron, lithium, and sodium elemental profiles suggest that there is little if any transport control within the alteration layer. These results are similar to those found for basalt glass. However, the correlation between the Li and Na profiles and that of a water species suggest that the limiting release is not controlled by the formation of the gel but rather is a steady state between the diffusion of a water species and matrix dissolution that results in a low release rate for alkali and this provides a steady driving force for the long-term dissolution of glass.

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H3O)(UO2)(PO4)·3H2O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. We have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

Dissolution of simplified nuclear waste glass and formation of secondary phases

Abstract. Immobilization of high-level and intermediate-level nuclear wastes by vitrification in borosilicate glass is a well-established process. There is a consensus between the waste management agencies of many countries and many experts that vitrified nuclear waste should be disposed of in a deep geological waste repository and therefore its long-term behavior needs to be taken into account in safety assessments. In contact with water, borosilicate glass is metastable and dissolves. In static dissolution experiments, often a surface alteration layer (SAL) forms on the dissolving glass, and later sometimes secondary phases form. Based on boron or lithium release rates, commonly three stages of glass dissolution are defined as a function of the reaction progress: (I) initial dissolution, described by a congruent glass dissolution at the highest rate, (II) residual dissolution, characterized by a glass dissolution rate several orders of magnitude lower than the initial one, and (III) resumption of glass alteration with initial rates. Microscopically, the formation of a complex SAL has been identified as a prerequisite for the slower dissolution kinetics of stage II. Stage III is typically observed under specific conditions, i.e., high temperature and/or high pH driven by the uptake of Si and Al into secondary phases. Different glass dissolution models explaining the mechanisms of the SAL formation and rate-limiting steps have been proposed and are still under debate. In this article different aspects of glass dissolution from recent studies in the literature and our own work are discussed with a focus on the microscopic aspects of SAL formation, secondary phase formation and the resumption of glass dissolution. Most of the experiments in the literature were performed under near-neutral pH conditions and at 90 ∘C, following standard procedures, to understand the fundamental mechanisms of glass dissolution. The example of interaction of glass and cementitious materials as discussed here is relevant for safety assessments because most international concepts include cement e.g., as lining, for plugs, or as part of the general construction of the repository. The aim of the investigations presented in this paper was to study the combined effect of hyperalkaline conditions and very high surface area/volume ratios (SA/V=264000m-1) on the dissolution of international simplified glass (ISG) and the formation of secondary phases at 70 ∘C in a synthetic young cement water containing Ca (YCWCa). The new results show that the SA/V ratio is a key parameter for the dissolution rate and for the formation of the altered glass surface and secondary phases. A comparison with similar studies in the literature shows that especially on the microscopic and nanoscale, different SA/V ratios lead to different features on the dissolving glass surface, even though the SA-normalized element release rates appear similar. Zeolite and Ca-silicate-hydrate phases (CSH) were identified and play a key role for the evolution of the solution chemistry. A kinetic dissolution model coupled with precipitation of secondary phases can be applied to relate the amount of dissolved glass to the evolution of the solution's pH.

Estimating Internal Stress of an Alteration Layer Formed on Corroded Boroaluminosilicate Glass through Spectroscopic Ellipsometry Analysis.

Aqueous corrosion of glass may result in the formation of an alteration layer in the glass surface of which chemical composition and network structure are different from those of the bulk glass. Since corrosion occurs far below the glass-transition temperature, the alteration layer cannot fully relax to the new structure with the lowest possible energy. Molecular dynamics simulations suggested that such a network will contain highly strained chemical bonds, which can be manifested as a stress in the alteration layer. Common techniques to measure stress in thin films or surface layers were found inadequate for thick monolithic glass samples corroded in water. Here, we explored the use of spectroscopic ellipsometry to test the presence of internal stress in the alteration layer formed by aqueous corrosion of glass. A procedure for analyses of spectroscopic ellipsometry data to determine birefringence in the alteration layer was developed. Findings with the established fitting procedure suggested that a stress builds up in the corroded surface layer of a boroaluminosilicate glass if there is a change in relative humidity, pH, or electrolyte concentration of the environment to which the glass surface is exposed. A similar process may occur in other types of glass, and it may affect the surface properties of corroded glass objects.

Enrichment and distribution of elements in the middle Miocene coal seams in the Orhaneli coalfield (NW Turkey)

This study focuses on ascertaining controlling factors and differences on mineralogical and elemental contents for reconstructing palaeoenvironmental conditions of both seams applying standard coal characteristics, mineralogical, coal-petrologic, and elemental data of the Orhaneli coalfield. The studied coalfield, one of the important coalfields in NW Turkey, includes two workable coal seams, the lower with 0.5–2 m and the upper with 5–6 m in thickness, which are separated by 2–5 m thick, grayish-green limnic claystone. The floor rocks of the both seams are limnic claystones, whereas the roof rock of the upper seam is the tuffite layers-bearing lacustrine marls. Matrix and xylite-rich lithotypes are common in the upper seam, while alternations of xylite-clayey bands (detro-xylite and xylo-detritic) are common in the lower seam. The lower seam is also characterized with the presence of altered tuff layers, while freshwater gastropod shell-bearing bands were identified from the upper seam. Even though the banding character and maceral composition of the coals were invariant between the seams, there are distinct differences in mineralogy and elemental composition, that can be related to the nature of the clastic sediment influx and contemporary volcanic inputs into freshwater forested mires.The lower seam is characterized by high ash yields (%44.2–64.3, d) and relatively high concentrations of aluminosilicate-affiliated elements and REY (rare earth elements and Y). In contrast, the upper seam has relatively low ash yield, and is slightly enriched B concentration. The B enrichment in the upper seam is presumably controlled by the presence of clay mineral (e.g., illite) and clastic volcanogenic accessory minerals (e.g., apatite). Arsenic is the only enriched element in both seams due to development of anoxic conditions. Although no traceable As was detected from syngenetic framboidal pyrite grains, the contemporary volcanic inputs (e.g., air-fall ash/tephra) along with leached surface waters into palaeomires might be source for As, while the development of anoxic conditions palaeomires could cause formation of syngenetic pyrite grains. Thus, the As concentrations of the studied samples are elevated. Nevertheless, the difference on ash yields and mineralogical compositions between studied seams might be related with different clastic influx ratios and contemporary volcanic inputs, in turn, aluminosilicate affiliated elements display different concentration coefficients (CC) values in the studied seams, and high B concentrations that are not expectable for a limnic coal Besides, enrichment of Cr, V and Ni in the upper seam are controlled by clastic V-bearing chromite grains from Orhaneli chromite deposit in the adjacent area. Furthermore, the contemporary volcanic inputs into the palaeomire of the lower seam, and their alteration under anoxic conditions caused REY enrichment and the formation of kaolinite and smectite matrices of clay aggregates in coal and altered tuff layers in this seam.

Temperature dependent lithium isotope fractionation during glass dissolution

Understanding the mechanisms by which borosilicate glasses corrode in contact with aqueous solutions remains a challenge to the safety case for the geological disposal of vitrified high-level nuclear waste. Here, lithium isotope fingerprinting techniques were applied to the leachates of a simulant Magnox waste glass to probe the mechanisms of aqueous corrosion at both short and long timescales (6 hours to 464 days). Experiments took place at 40 and 90 °C to assess the consistency of the dissolution mechanisms across a range of commonly employed temperatures and the legitimacy of applying higher temperature experimental datasets to understand glass corrosion within a disposal facility at lower temperatures.Two competing release mechanisms were observed for lithium (diffusion and hydrolysis), and the relative proportions of these mechanisms changed through time. Leachates initially had lower δ7Li values than the pristine glass (−2.7‰ at 40 °C and −1.1‰ at 90 °C relative to the pristine glass) at both temperatures due to lithium leaching incongruently through diffusive processes. The greater offset between solution and solid at lower temperatures indicates a larger rate of diffusion (incongruent dissolution) relative to the rate of hydrolysis (congruent dissolution) at lower temperatures. The fraction of lithium released through diffusion relative to the fraction of lithium released through hydrolysis then increased at both temperatures with time up to 126 days, increasing from 0.47 and 0.22 at 6 hours to 0.66 and 0.41 at 126 days at 40 and 90 °C respectively. Subsequently, the fractions of lithium released through diffusion sharply decreased to 0.36 at 40 °C and 0.22 at 90 °C after 464 days, consistent with network hydrolysis coupled with secondary phase precipitation later controlling the long-term release of Li at both temperatures. Throughout the duration of the experiments (464 days) the δ7Li values in solution increased to 9.0‰ at 40 °C and 10.0‰ at 90 °C due to the formation of talc and montmorillonite phases at 40 °C and additional smectite phases at 90 °C. Further, no evidence for the formation of a diffusive barrier to the transport of Li within the alteration layers became apparent during the later stages of dissolution at either temperature. However, the fraction of lithium leached through diffusion was still significant throughout all stages of dissolution. Lithium isotope ratios in solution were correlated with the transition from a system which was increasingly dominated by lithium diffusion as the dissolution rate slowed to one which was controlled by hydrolysis coupled with secondary phase precipitation at long durations. Alongside elemental ratios in solution, these results were consistent with the same set of mechanisms governing dissolution across the temperature range studied.

Tailoring effect of Y2O3 on water resistance of Na2O–ZnO–Al2O3–B2O3 glasses

To explore the improving effect of Y2O3 on the water resistance of xY2O3-(100–x)(0.05Al2O3-0.15ZnO-0.15Na2O-0.65B2O3) (x = 0, 0.7 mol%, 1.4 mol%, 2.1 mol%, 2.8 mol%) glasses, glass structure and ion migration characteristics were respectively characterized by an infrared spectrometer and an electrochemical workstation. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and inductively coupled plasm-atomic emission spectrometry (ICP-AES) were used to comprehensively analyze the alteration products. The experimental results show that with the increase of Y2O3 content, the mass loss per unit area of the glass is significantly reduced, and pH in leaching solution has the same change trend with mass loss of the glass, which indicates the improving effect of Y2O3 addition on the studied glass. The content of [BO4] structural unit and dc conductivity of glass increase firstly and then decrease with the increase of Y2O3 content, and reach a maximum at x = 0.7 mol%. Although addition of Y2O3 plays the role in the changes of glass structure and ion migration characteristics, the more important influence of Y2O3 is on the glass surface alteration layer. Y and Zn elements are enriched on the glass surface and finally transformed into an alteration layer, moreover, the adhesion between the alteration layers and the glass matrix is enhanced with the increase of Y2O3 content, which effectively blocks the further interdiffusion between the water molecules and the glass matrix.

Influence of artificial aging on corrosion of abraded Al-Zn-Mg-Cu alloys

Surface abrasion has been shown to create altered surface layers (ASLs) that are hundreds of nm thick on all types of Al alloys. Such ASLs have lower corrosion resistance than the underlying substrate of Al-Zn-Mg-Cu alloys. Here, we demonstrate how heat treatments affect the ASL microstructure on abraded Al-Zn-Mg-Cu alloys using transmission electron microscopy and atom probe tomography, and also how the corrosion properties change using electrochemical polarization. High temperature treatments on the abraded bulk samples enhance η phase precipitation in the ASL, leading to a decreased Zn content in the ASL solid solution, which ennobles the ASL breakdown potential.

Characterization of medieval-like glass alteration layers by laser spectroscopy and nonlinear optical microscopy

Historical glass-based objects undergo, since the time of their manufacture, different degradation phenomena that are related to their composition and to the environment to which they were exposed. Three-dimensional (3D) structural and chemical characterization of the degradation layers is important to select the most adequate conservation strategies for glass objects. Optical microscopy (OM) is the most frequently used non-destructive method to examine the surface of historical glasses; however, the 3D structural assessment of alteration layers requires applying the destructive modality of this technique to conduct a cross-sectional study. In this work, a different approach for structural and compositional characterization of alteration layers on model medieval-like glasses is presented, based on the combination of the laser spectroscopies of laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF) and FT-Raman, and the emerging, cutting edge technique of nonlinear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF). The results obtained through this multi-analytical photonic approach were compared with those retrieved by examination of the surface and cross sections of the samples by OM and scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM–EDS). While the combination of LIBS, LIF and FT-Raman served to assess the composition of the various alteration layers, the use of MPEF microscopy allowed the non-destructive determination of the thicknesses of these layers, showing for both thickness and composition a good agreement with the OM and SEM–EDS results. Thus, the proposed approach, which avoids sample preparation, illustrates the capability of non-destructive, or micro-destructive in the case of LIBS, laser spectroscopies and microscopies for the in situ study of glass objects of historic or/and artistic value.Graphic

Corrosion of ternary borosilicate glass in acidic solution studied in operando by fluid-cell Raman spectroscopy

Fluid-cell Raman spectroscopy is a space and time-resolving application allowing in operando studies of dynamic processes during solution–solid interactions. A currently heavily debated example is the corrosion mechanism of borosilicate glasses, which are the favoured material for the immobilization of high-level nuclear waste. With an upgraded fluid-cell lid design made entirely from the glass sample itself, we present the polymerization of the surface alteration layer over time in an initially acidic environment, including the differentiation between pore and surface-adsorbed water within it. Our results support an interface-coupled dissolution-precipitation model, which opposes traditional ion-exchange models for the corrosion mechanism. A sound description of the corrosion mechanism is essential for reliable numerical models to predict the corrosion rate of nuclear waste glasses during long-term storage in a geological repository.

Subsurface temperature estimation in a geothermal field based on audio-frequency magnetotelluric data

In geothermal exploration, the subsurface temperature distribution is an important parameter since it is closely related to the existing geothermal system. However, subsurface temperature information can only be obtained from boreholes, requiring a considerable cost and a limited number. A new geothermometry technique based on the relationship between temperature and resistivity has been proposed to overcome this difficulty. In order to enhance the reliability of this method, the subsurface heat condition in a different geological and geographical location was reconstructed. The temperature up to some depth beneath the surface could be estimated incorporating the back-propagation neural network using resistivity determined by high-resolution audio-magnetotelluric soundings. The temperature profiles resulting from the neural network fit with those observed from nearby boreholes, providing a satisfying evaluation result of the model’s predictive powers. Joint interpretation was then carried out following the one-dimensional resistivity inversion result and temperature cross-section. Both resistivity and temperature anomalies show an excellent agreement, so that subsurface anomaly such as altered layers, reservoir zone, and some possible faults was detected. With an appropriate training strategy, this technique can help to significantly reduce the costs at estimating the subsurface temperature.

Effects of Al:Si and (Al+Na):Si ratios on the static corrosion of sodium‐boroaluminosilicate glasses

AbstractUnderstanding alteration mechanisms of borosilicate glasses in aqueous media is essential to nuclear waste performance assessments to ensure radioisotopes are contained for extended durations. Aluminum is typically added to glass compositions to reduce the extent of alteration. However, previous work on 7‐day durability tests has suggested that Al has a nonlinear relationship with extent of alteration. The effects of Al:Si and (Al+Na):Si substitutions on glass durability were evaluated using series of glasses based on the International Simple Glass corroded in static conditions up to 13 months in deionized water at 90°C. The alteration behavior was determined by measurement of element release in solution. The ⁓7‐day alteration trends across the series were consistent with predicted trends. The 13‐month results indicated overall alteration decreased as Al:Si ratios increased and was unaffected by changes in (Al+Na):Si except for the glass with the highest (Al+Na):Si ratio (ISG‐A23N), which completely altered within 14 days. Frequent sampling and in situ Raman measurements of solutions revealed ISG‐A23N experienced several distinguishable alteration rate regimes within 7 days, forming a ⁓100 µm alteration layer and a NaSiAlO4 zeolite.

Defining a Non-Destructive In Situ Approach for the Determination of Historical Mortar Strength Using the Equotip Hardness Tester

The determination of mechanical parameters of historical mortars is a crucial aspect in the analysis of masonry in ancient buildings, especially for evaluating their quality and planning the appropriate restoration interventions. Due to conservation reasons, creating a comprehensive database is generally not possible because cutting out masonry specimens relates to damaging historical structures. This study starts with the need to characterize the mortar quality of different buildings in the town of Camerino (Central Italy) which has been strongly damaged by the 2016–2017 seismic sequence. A non-destructive collecting data strategy based on the use of the Equotip hardness tester (EQ) has been set up by evaluating the most appropriates impact strategy (single or repeated) and the range of measurements to calculate the basic statistics. The seismic damage suffered by the buildings allowed the rare opportunity to take samples from several walls and carry out laboratory tests to determine their Uniaxial Compressive Strength (UCS). The comparison between the results of the two types of tests made it possible to calibrate a relationship between the EQ values and the UCS. The Pearson’s coefficient of determination derived from an exponential interpolation (R2 = 0.81) confirmed a strong relationship between the EQ values derived from the tests on the specimens and the UCS. Moreover, comparing the in situ EQ measurements with the ones performed on the specimens prepared for the compressive tests, a general underestimation of the in situ EQ values has been observed, possibly due to the presence of a superficial alteration layer of the exposed mortar. From these results, we propose a correction of the in situ measurements able to obtain a more appropriate strength estimate of the historical mortars.

Interface induced diffusion

Interface induced diffusion had been identified in a thin film system damaged by electron bombardment. This new phenomenon was observed in Al2O3 (some nm thick)/Si substrate system, which was subjected to low energy (5 keV) electron bombardment producing defects in the Al2O3 layer. The defects produced partially relaxed. The rate of relaxation is, however, was different in the vicinity of the interface and in the "bulk" parts of the Al2O3 layer. This difference creates an oxygen concentration gradient and consequently oxygen diffusion, resulting in an altered layer which grows from the Al2O3/Si substrate interface. The relative rate of the diffusion and relaxation is strongly temperature dependent, resulting in various altered layer compositions, SiO2 (at room temperature), Al2O3 + AlOx + Si (at 500 °C), Al2O3 + Si (at 700 °C), as the temperature during irradiation varies. Utilizing this finding it is possible to produce area selective interface patterning.

Fusion of ASTER satellite imagery, geochemical and geology data for gold prospecting in the Astaneh granite intrusive, West Central Iran

ABSTRACT In this study, ASTER imagery, geochemical, lithological, and structural data are exploited for Mineral Potential Mapping (MPM) of the Astaneh granitic pluton and its surrounding area. The independent component analysis (ICA) and Matched Filtering (MF) techniques are applied to ASTER data for detecting alteration mineral assemblages. Sericitically argillically altered minerals associated with jarosite and chlorite/epidote are mapped using the ICA technique. MF fraction images derived from n-dimensional visualisation (n-DV) tool facilitated detecting goethite, haematite, limonite, muscovite, kaolinite, illite, chlorite and epidote associated with gold occurrences. The distribution of Cu, Pb, Zn and Au is considered for generating geochemical anomaly layers. Strong Cu, Zn and Au anomalies are found to be associated with gold mineralisation. The lithological units hosting gold mineralisation and intersection of NE–SW and NW–SE trending lineaments are also considered. Fuzzy Logic Model (FLM) was used to generate gold prospectivity map for the study area by fusing the alteration, geochemical, geology and structural layers. Several high prospective zones are identified in the central and southeastern part of the study area. A majority of delineated exploration targets are either linked to the plutonic body or its surrounding metamorphic rocks. This study demonstrated a viable approach for future gold prospecting in the study area.

The fate of Si and Fe while nuclear glass alters with steel and clay

The French concept developed to dispose high-level radioactive waste in geological repository relies on glassy waste forms, isolated from the claystone host rock by steel containers. Understanding interactions between glass and surrounding materials is key for assessing the performance of a such system. Here, isotopically tagged SON68 glass, steel and claystone were studied through an integrated mockup conducted at 50 °C for 2.5 years. Post-mortem analyses were performed from nanometric to millimetric scales using TEM, STXM, ToF-SIMS and SEM techniques. The glass alteration layer consisted of a crystallized Fe-rich smectite mineral, close to nontronite, supporting a dissolution/reprecipitation controlling mechanism for glass alteration. The mean glass dissolution rate ranged between 1.6 × 10−2 g m−2 d−1 to 3.0 × 10−2 g m−2 d−1, a value only 3–5 times lower than the initial dissolution rate. Thermodynamic calculations highlighted a competition between nontronite and protective gel, explaining why in the present conditions the formation of a protective layer is prevented.