Mineral Layers Research Articles

Biomimetic Remineralization of Dental Hard Tissues via Amyloid‐Like Protein Matrix Composite with Amorphous Calcium Phosphate

AbstractNumerous remineralizing coatings aim to prevent or treat early enamel lesions and occlude exposed dentinal tubules (DTs). Nevertheless, the pace of remineralization is inadequate, and the mechanical robustness of the newly established mineral layer fails to match the inherent strength. In this study, a biomimetic mineralization strategy aimed at replicating key events in biological mineralization, specifically focusing on the organic–inorganic composite matrix, is proposed. The material utilizes Tris(2‐carboxyethyl)phosphine (TCEP), which serves a dual role: stabilized amorphous calcium phosphate (ACP) (ACP@TCEP) nanoparticles as its inorganic component, and catalyzing the cleavage of intramolecular disulfide bonds in poly(ethylene glycol) (PEG) grafted lysozyme (lyso‐PEG) to facilitate the formation of an amyloid‐like protein matrix composite with ACP (ACP@lyso‐PEG nanocomplexes). ACP@lyso‐PEG nanocomplexes can rapidly and efficiently form an enamel‐like remineralization layer on the surface of damaged dental hard tissue, reaching ≈4.205 µm thickness after 3 days of acid‐etched enamel. Furthermore, achieving a depth of DTs occlusion exceeding 60 µm after 5 days, using a simple immersion process. The resulting mineralized layer exhibits mechanical strength comparable to natural teeth. This study introduces a conceptual biomimetic mineralization strategy for effective enamel repair or DTs occlusion in clinical practices, and offers potential insights into the mechanisms of biomineral formation.

Long-term impact of wildfire on soil physical, chemical and biological properties within a pine forest

AbstractAnthropogenic fires pose a serious threat to many terrestrial ecosystems because they can cause loss of biodiversity and carbon stocks in the biosphere. Specifically, wildfires impacting natural conservation areas such as European Natura 2000 sites (N2K) are of particular concern. The main study objective was to evaluate the long-term effects of wildfires on the organic layer and some physical, chemical and biological properties of the underlying soil mineral layer, linked to soil quality. Here, we studied two coastal Mediterranean Aleppo pine stands within an N2K site differing for the fires’ years of occurrence, the time between fires (TBF) and the time since last fire (TSLF) throughout 24 years. Furthermore, in each stand, differences in fire frequency (FF) were considered by selecting three sites—double-fire, single-fire and control (unburnt). Our results show the absence of the O-layer in double-fire sites, indicating a loss of this organic carbon (if compared to control) pool of 204 g m−2 in R2F and 139 g m−2 in M2F. Despite this loss being offset by the Corg increase in soil mineral layer, the disappearance of O-layer may compromise the ecosystem services provided by soil. In each stand, long-term fire effects were evident at both single-fire and double-fire sites for some chemical as well as biological soil properties and depended on TSLF. Increased rates of nitrogen mineralization and nitrification were found at all burned sites, persisting up to 24 years post-fire. Soil quality indicators data highlighted the recovery handicap of the microbial community within the considered period. Since our outcomes showed wildfires enduring consequences, mainly relating to TSLF and FF, on different organic and mineral soil properties, we advocate employing prompt strategies to mitigate recurring fires.

Long-term behaviour of Cs-137, Cs-133 and K in beech trees of French forests

In the long-term after atmospheric deposit onto a forest ecosystem, Cs-137 becomes incorporated into the biogeochemical cycle of stable elements and progressively reaches a quasi-equilibrium state. This study aimed at determining to what extent Cs-137 activity distribution in tree vegetation could be predicted from that of stable caesium (Cs-133) and potassium (K), which are known to be stable chemical analogues and competitors for Cs-137 intake in tree organs. Field campaigns that focused on beech trees (Fagus sylvatica L.) were conducted in 2021 in three French forest stands with contrasted characteristics regarding either the contribution of global vs. Chornobyl fallouts, soil or climatic conditions. Decades after Cs-137 fallouts, it was found that more than 80% of the total radioactive inventory in the system remained confined in the top 20 cm mineral layers, while organic layers and beech vegetation (including roots) contributed each to less than 1.5%. The enhanced downward migration of Cs-137 in cambisol than podzol forest sites was presumably due to migration of clay particles and bioturbation. The distribution of Cs-137 and Cs-133 inventories in beech trees was very similar among sites but differed from that of K due a higher accumulation of Cs isotopes in roots (40–50% vs. < 25% for K). The aggregated transfer factor (Tag) of Cs-137 calculated for aerial beech organs were all lower than those reported in literature more than 20 years ago, this suggesting a decrease of bioavailability in soil due to ageing processes. Regarding their variability, Tags were generally lower by a factor 5 at the cambisol site, which was fairly well explained by a much higher value of RIP (radiocesium immobilisation potential). Cs-137 concentrations in trees organs normalized by the soil exchangeable fractions were linearly correlated to those of Cs-133 and the best fit was found for the linear regression model without intercept indicating that no more contribution of the foliar uptake could be observed on long term. Provided that the vertical distribution of caesium concentrations and fine root density are properly measured or estimated, Cs-133 was shown to be a much better proxy than K to estimate the root transfer of Cs-137.

In-silico investigation of mechanical behavior of hydrated Na-montmorillonite tactoid

Swelling clay minerals, exemplified by Na-montmorillonite (Na-Mt), are vital constituents in expansive soils and hold significant relevance in geotechnical engineering. Comprehending their distinctive swelling behavior upon hydration is imperative for managing potential damage to civil infrastructure. Conversely, this swelling property gives rise to numerous advantageous applications, including using these clays in barrier materials and nanocomposites. The hierarchical structure of montmorillonite, consisting of clay mineral layers, tactoids, aggregates, and assemblies of aggregates, plays a pivotal role in the swelling behavior of expansive clays. This investigation employs molecular dynamics (MD) and steered molecular dynamic (SMD) simulations to explore the nanomechanical properties of hydrated Na-Mt tactoids at various hydration levels. It provides insights into their responses to compression, tensile, and shear deformation. This study reveals increased hydration levels increase interlayer spacing in clay structures, resulting in higher average d‐values. Water molecules drive attractive electrostatic interactions with clay mineral layers, predominantly mediated by sodium ions, highlighting the complex interplay between interlayer hydration and tactoid stability. Higher hydration enhances tactoid compressibility, reducing the stress required for deformation by compressing water molecules and clay mineral layers in the interlayer space. The study also demonstrates a notable reduction in tensile modulus with increasing hydration, signifying the significant impact of even minimal hydration on interlayer cation-clay layer interactions. Hydrated tactoids exhibit altered mechanical responses in shear deformation compared to dry ones, requiring lower shear stress to detach the top clay layer from the tactoid. The presence of water molecules impedes the locking of clay mineral layers, further influencing mechanical properties. The results and insight provided by this work will contribute to a better understanding of the impact of interlayer hydration on the stability and response of swelling clay minerals.

The migration and occupation of Li+ and Na+ in illite and montmorillonite during the heating process

Abstract The impact of temperature on the migration of cations within layers of clay minerals is of profound significance for the design and practical application of materials derived from clay minerals. This study focuses on Li+ and Na+ as representative cations, together with illite (Ilt) and montmorillonite (Mnt) as representative clay minerals. The study investigates the behaviour of cation migration and occupation within clay minerals across varying temperatures. A series of samples were prepared meticulously by immersing illite and montmorillonite in Li+ and Na+ solutions, subsequently subjecting them to different temperatures (unheated, 100, 150, 200, 250 and 300°C) for 24 h. Through the use of techniques such as X-ray diffraction (XRD), cation exchange capacity (CEC), Fourier-transform infrared spectroscopy (FTIR), magic angle rotating solid nuclear magnetic resonance spectroscopy (MAS NMR), and X-ray photoelectron spectroscopy (XPS), the study discerns structural transformations in illite and montmorillonite, and tracks the migration and occupation of Li+ and Na+. The findings reveal that following heating, Na+ and Li+ do not infiltrate the lattice of illite. For montmorillonite, Na+ also does not migrate into the montmorillonite lattice, however, in contrast, Li+ does exhibit migration into this lattice. Notably, the migration and occupation of interlayer Li+ within montmorillonite exhibit discernible temperature dependence. Specifically, upon reaching 150°C, interlayer Li+ migrate to ditrigonal cavities within the tetrahedral layers. As the temperature elevates to 200°C, Li+ further permeate vacant octahedral sites through the ditrigonal cavities, culminating in the formation of a localised trioctahedral structure.

Aggregated database of forest soil chemical properties in the Czech Republic based on surveys from 2000 to 2020

Key messageThe dataset includes data from forest soil surveys conducted in the period 2000–2020. It provides soil and site variables from 8269 locations. Data are aggregated in three basic soil layers: upper organic soil horizon (FH, 6875 locations), upper mineral layer 0–30 cm (M03, 8051 locations) and deeper mineral soil layer 30–80 cm (M38, 2260 locations).The dataset is available at https://doi.org/10.5281/zenodo.10608814, and access to the metadata is at https://metadata-afs.nancy.inra.fr/geonetwork/srv/fre/catalog.search#/metadata/38f24573-3c0d-469a-a66a-7060ce082155.

Impact of rock heterogeneity on reactive flow during acid stimulation process

Acid stimulation within carbonate rocks represents a crucial aspect of reactive flow applications in subsurface porous media and has been widely used in carbonate reservoir development attributed to its rapid effectiveness and cost-efficiency. This study is motivated to investigate further the impact of rock heterogeneity on the acid stimulation process. The two-scale continuum model is employed for capturing mass, momentum, and energy transfer during the acid stimulation process. The core-scale model is expanded to consider the specific composition of solid minerals, including reactive minerals such as calcite and dolomite and non-reactive ones like quartz and clay. A heterogeneity generator is developed by coupling with the open-source geostatistical program to produce different heterogeneous parameters using random seeds with varying spatial correlation lengths. Sensitive cases are performed to present an investigation into the influence of mineral composition and matrix heterogeneity on the acid stimulation process. Results show that the typical results of acid stimulation are closely tied to different heterogeneity conditions. The optimum conditions for acid stimulation are sensitive to the concentration of reactive components. The optimum acid injection rate declines as dolomite content increases, while the corresponding acidizing breakthrough volume reduces with higher calcite levels. The presence of mineral layers, especially in horizontal distributions, complicates acid fluid efficiency due to the competitive reaction between calcite and dolomite. Compared to the heterogeneous distribution of minerals, matrix heterogeneity plays a critical role in acid fluid consumption efficiency. Increasing heterogeneity leads to significant reductions in breakthrough volumes, largely governed by the correlation length.

Biomimetic Mineralized 3D-Printed Polycaprolactone Scaffold Induced by Self-Adaptive Nanotopology to Accelerate Bone Regeneration.

Three-dimensional (3D)-printed biodegradable polymer scaffolds are at the forefront of personalized constructs for bone tissue engineering. However, it remains challenging to create a biological microenvironment for bone growth. Herein, we developed a novel yet feasible approach to facilitate biomimetic mineralization via self-adaptive nanotopography, which overcomes difficulties in the surface biofunctionalization of 3D-printed polycaprolactone (PCL) scaffolds. The building blocks of self-adaptive nanotopography were PCL lamellae that formed on the 3D-printed PCL scaffold via surface-directed epitaxial crystallization and acted as a linker to nucleate and generate hydroxyapatite crystals. Accordingly, a uniform and robust mineralized layer was immobilized throughout the scaffolds, which strongly bound to the strands and had no effect on the mechanical properties of the scaffolds. In vitro cell culture experiments revealed that the resulting scaffold was biocompatible and enhanced the proliferation and osteogenic differentiation of mouse embryolous osteoblast cells. Furthermore, we demonstrated that the resulting scaffold showed a strong capability to accelerate in vivo bone regeneration using a rabbit bone defect model. This study provides valuable opportunities to enhance the application of 3D-printed scaffolds in bone repair, paving the way for translation to other orthopedic implants.

The tire–road contact: A mechanical mixing seen as a shear-induced diffusive process

In this paper, the mechanical mixing of road minerals and tire tread rubber is studied experimentally and numerically. A rubber specimen on an experimental set-up is used. SEM observations show that particles on the surface are composed of an intimate mixture of rubber compounds and minerals. A longitudinal section is also observed, showing that the minerals have migrated into the surface. This phenomenon can be seen as a diffusive process driven by shear. To understand the underlying mechanisms, a numerical model is proposed using soft bodies to represent the rubber top layer. A layer of minerals is then sheared onto this surface. The minerals migrate progressively into the rubber, forming a mixed layer of rubber and minerals. The results show also that the mixing mainly depends on the shear rate in the layer containing the minerals. Due to a reinforcing effect of the minerals, velocity is increasingly accommodated in the layer without minerals. As a result, the shear rate in the mixed layer decreases, and therefore the mineral migration. This coupled mechanism explains why the mixing process stops before reaching a homogenized state in the entire domain. To support this analysis, a diffusion coefficient is derived as a function of the shear rate in the mixed layer.

Multiple isotopes reveal the impact of land use change on nitrate transport and transformation in deep loess deposits

The deep-rooted economic trees decrease water storage but increase nitrate-nitrogen (NO3–N) accumulation in the soil due to the root water uptake and excessive use of fertilizers. Knowing how the NO3 accumulates in the soil and to what extent it can be flushed out or transformed can provide insights on the processes controlling N flux to waterways. We sampled cultivated farmland and orchards with varying ages of apple and peach trees in the loess deposits to > 15 m depth to measure the contents and isotopes of water and NO3 in soils. The novelty of this study is that the water isotopes are used to analyze water and NO3 transport, while the NO3 isotopes are further employed for NO3 source and transformation analysis. The parabolic NO3–N profiles (258–3579 kg N ha−1) were mainly observed within 0–5 m under different land use types. The surface-aggregated NO3 reservoirs under old apple orchard were about six times of farmland due to the overuse of chemical fertilizers, while those of peach orchard were only half of farmland because of less fertilizer inputs and possible root absorption effects. Piston flow resulted in the overall slow water movement and low NO3 flux under different land use types in deep loess deposits. Despite the soil water recharge by precipitation and low surface evaporation, the strong transpiration effects further resulted in no water and NO3 fluxes in the deep layers under old apple orchard. Nitrate reservoirs were mainly contributed by soil organic N (44 % ± 26 %) and ammonium N fertilizer (36 % ± 20 %), but their transformation was dominated by nitrification under old apple orchard and by mineralization in deep layers. The risks of NO3 bombs are temporarily weakened by lower dried soil layers under deep rooted plants; however, with lower water movement rates and limited denitrification potential, NO3 would eventually reach the aquifers in a few hundred years or more. This study provides new insights for clarifying NO3 transport and transformation processes by combing multiple isotopes, and the NO3 bombs would chronically endanger the sustainable development of terrestrial ecosystems and the environment in arid regions.

Hydrophilicity of Organically Modified Montmorillonite and Effect on Benzene Adsorption by the Molecular Dynamics Method.

Interlayer modification of layered materials with organocations has been known to endow the nanocomposite with hydrophobicity, and adsorption of aromatic compounds in the aqueous phase has been investigated for decades by using montmorillonite, a representative layered clay mineral, as the host material. Usage of the organocation has been believed to be effective due to the π-π interaction with the aromatic adsorbate, the presence of which is not verified spectroscopically in the water-immersed state. Considering that the organocation is generally regarded as a pillar to keep the interlayer space, the interaction between the organocation and adsorbate has not yet been clarified sufficiently. In the present study, we revealed the role of the organocation by the molecular dynamics method, where tetramethylammonium (TMA) and trimethylphenylammonium (TMPA) ions were selected as the representative and simple organocations, and benzene was the adsorbate to exclude the effect of the substitution group. Both H2O and benzene molecules were introduced in the interlayer of TMA- or TMPA-modified montmorillonite to model the water-immersed adsorption structure. It was found that H2O is preferentially distributed on the clay surface, followed by the center of the interlayer when the amount of H2O is large. In the adsorption model, benzene was vertically adsorbed on the clay surface. Radial distribution function analysis revealed that benzene is distributed around both the methyl and the phenyl groups in the TMA and TMPA cations, but the orientation of the phenyl ring is not consistent with that of benzene. Thus, benzene was found not to form the π-π interaction in montmorillonite modified with the TMPA cations in the water-immersed state. Furthermore, the surface was partly covered with the phenyl group in the TMPA cation, decreasing the adsorption area. Therefore, the experimental suggestion that benzene is adsorbed on the clay surface was reproduced by our simulation, and the interaction between the organocation and benzene and surface occupancy should be paid attention to maximize the adsorption property.

Post-fire soil greenhouse gas fluxes in boreal Scots pine forests–Are they affected by surface fires with different severities?

Although forest fires are one of the main natural disturbance types in boreal forests, there is limited information regarding surface fires (dominant in Northern Europe), and how surface fires of different severities could affect post-fire soil greenhouse gas emissions. The results of our study show that fire severity, time since fire and post-fire changes in soil temperature were the main factors driving soil carbon dioxide (CO2) flux (forest floor ecosystem respiration) from burned boreal forest soils. Approximately two hours after the fire, soil CO2 emissions from burned areas were significantly higher compared to pre-fire conditions, and areas with high-severity fires had significantly higher soil CO2 emissions compared to those with low-severity fires. Later (days, months) after the fire, the unburned control areas always had higher soil CO2 emission values compared to burned areas. In the case of methane (CH4), time since fire and post-fire changes in soil temperatures were the main factors driving soil CH4 fluxes. Unburned study areas were sinks of CH4 through the entire measurement period, while immediately after the fire, the burned areas turned from CH4 sink to CH4 source. For nitrous oxide (N2O) measurements, time since fire was the only factor that significantly affected soil N2O fluxes. Shortly after the fire, N2O emissions increased significantly from both low- and high-intensity study plots. Two days after the fire, post-fire soil C and N content decreased in the O-horizon and increased within the first 5 cm of the soil mineral layer, and the trend was visible both in low- and high-severity fire plots. Samples collected four months after the fire, showed similar total soil C and N content as there was before the fire.

Exploring hydrological controls on dissolved organic carbon export dynamics in a typical flash flood catchment using a process-based model

The dynamics of dissolved organic carbon (DOC) export from headwater catchments are of critical importance for the global carbon balance and are driven by complex runoff processes. Most previous studies have used statistical relationships between runoff and DOC concentration to estimate DOC export dynamics. Thus, the coupling mechanisms between runoff generation and DOC export dynamics at the process level were obscured in the fitting parameters and have rarely been addressed. In this study, high-frequency (hourly) discharge and DOC export from a typical flash flood experimental headwater catchment with an area of 1.8 km2 were simulated using a process-based model (INCA-C). The results showed that the INCA-C model successfully captured the hourly dynamics of both discharge and DOC concentrations with a Nash–Sutcliffe efficiency (NSE) of 0.47–0.81 and 0.28–0.70 among moderate events and 0.81–0.85 and 0.19–0.90 among extreme events, respectively. The DOC was exported with distinct concentration dynamics, fluxes, and contributions from the four flow pathways under different storm intensities. At higher intensities, the DOC fluxes were exported by subsurface flows, particularly from shallow organic soil, with greater peaks and shorter time-to-peaks. Exported DOC is primarily sourced from subsurface runoff from the mineral layer (73 %–77 %) during moderate events, whereas it is primarily sourced from subsurface runoff from the organic layer (61 %–79 %) during extreme events. The two contrasting contributions suggest that hydrological pathway controls and DOC dynamic patterns can shift owing to runoff generation influenced by storm intensity. The distinct and variable controls of different flow pathways on DOC export highlight the need to explain the role of hydrology in regulating DOC storm exports through process-based modelling.

Similarities and differences among selected gemmological varieties of chalcedony: chemistry, mineralogy and microstructure

AbstractThis study describes a new variety of chalcedony with a unique inhomogeneous bluish green hue, named aquaprase. It was discovered in Africa and is considered to be a valuable addition to the gem trade. A multi-methodological approach was used to examine its chemistry, mineralogy and microstructure, which were then compared to those of chrysoprase and agate, two of the most popular varieties of chalcedony. Optical microscopy revealed a complex microstructural heterogeneity in the different colour intensity areas/bands of aquaprase and agate, whereas chrysoprase exhibited a more homogeneous coexistence of micro- and cryptocrystalline quartz. High-resolution synchrotron XRD was essential for highlighting the complex assemblage of various types of α-quartz in aquaprase and agate (which differ in terms of crystal size and/or cell parameters). Micro-Raman spectroscopy revealed α-quartz and moganite in all three varieties of chalcedony and the presence of the nickel-bearing layered silicate mineral, willemseite, in chrysoprase, which is responsible for its green colouration. The chemical analysis displayed a homogeneous composition of agate, as well as high levels of nickel content in the chrysoprase variety. Aquaprase showed significant amounts (ppm by weight) of trace elements (Al, Mg, Na, K, Ca, Ti, U and Fe) characteristic of its formation environment, as well as high values of Cr, which are thought to be the cause of its bluish green colouration.

Physicochemical Characteristics of Feldspar Deposits in Zango Daji, Kogi State Using Geological Methods

Six rock samples were randomly collected and photographs, locational coordinates and elevation points were taken with appropriate tools and devices. Portions of samples were prepared into thin sections and observed under hand lenses, microscope, tested for hardness and other diagnostic properties. Specific density was also determined. The remaining samples were subjected to geochemical and mineralogical analysis. An average percentage composition of 17.1958 mass % of K2O was obtained which is far greater than its Calcium and Sodium contents, indicating it is a K-feldspar. Geochemical result showed averages of Si2O, Al2O3, K2O, Na2O, CaO, and Fe2O3, contents of 59.54 mass %, 17.83 mass %, 17.19 mass %, 2.33 mass %, 0.08 mass % and 1.60 mass % respectively while mineralogical results revealed it is orthoclase in view of its high alumina content of 17.83 percent. The results showed that the sample specification meets the British International Standard specification. Furthermore, electrical resistivity tomography survey was conducted by setting up Schlumberger Electrode Array to determine the significant resistivity contrast between the feldspar and the compact bedrock in the profile. The resistivity data of eight points were processed into Resists curves after conversion and subjecting the data by inversion with WinResist software to obtain 1 - D and 2 – D maps. Together with results of chemical analyses and vertical electrical sounding, the location map of mineralogical composition of the Oxides were determined. Field and petrographic evidence showed a potential source of gemstones and niobium. The study also revealed the occurrence of feldspar deposit are hosted by granitic and pegmatitic intrusive. The quantum and reserve estimates of both overburden layer and target mineral thickness were determined to be 44.3 ± 2.18 million metric tons and 741,933 ± 132,205 m³ respectively.

Surface Modification of Montmorillonite Clay Towards the Fabrication of Nanocomposites for Engineering Applications

Montmorillonite (MMT) is a layered clay mineral composed of silica and alumina sheets with a layer thickness of about 1 nm qualifies it as a two-dimensional nanomaterial. MMT is found in natural clay ores in the Murunkan, Kirinda, and Okanda areas in Sri Lanka. Nanocomposites with enhanced physical and mechanical properties can be prepared by dispersing MMT in a polymer matrix. However, the hydrophilic nature of MMT hinders the incorporation of MMT into hydrophobic polymer matrices. Hence, a suitable surface modification is required to make MMT compatible with polymers. The present study was based on the preparation and analysis of organically modified calcium Montmorillonite (Ca-MMT)-polypropylene nanocomposites as a green technology initiative. Homo-ionic Ca-MMT was prepared by treating commercial MMT-K10 with a CaCl2 solution. The predominant exchangeable divalent cations present in MMT-K10 and Ca-MMT were determined using AAS. The cation exchange capacity of Ca-MMT was about two times greater than that of MMT-K10. Furthermore, XRD analysis showed a slight increase in d- spacing of Ca-MMT compared to MMT-K10. A novel ligand, triethylene glycol dodecyl methyl ether was synthesized by treating triethylene glycol monomethyl ether (TGME) with 50% w/w aqueous solution of sodium hydroxide followed by 1-bromododecane with the molar ratio of TGME:NaOH:1-bromododecane in 1:2:2. The crude product was purified by column chromatography and characterized by FTIR and GCMS analysis. Hydrophilic Ca-MMT was surface modified with the organic ligand presumably via the coordination of triethylene glycol moiety with Ca2+ cations at the outer edge of the MMT particles. The long aliphatic chains in the periphery of the modified MMT particle make it more organophilic. Modified Ca-MMT was characterized by XRD, TGA, and FTIR analysis. The XRD revealed a slight increase in the d-spacing related to the 001 plane of modified Ca-MMT compared to unmodified clay. The effect of modified Ca-MMT loadings (0.5%, 1%, and 1.5%) on the mechanical properties of the nanocomposite was studied. The results implied an enhancement of the mechanical properties in terms of impact resistance, hardness, and flexural properties in the nanocomposite compared to the virgin polymer. The fabricated nanocomposite is a promising engineering material that may have applications in automotive, construction, and packaging products.&#x0D; &#x0D; Keywords: Montmorillonite, Polypropylene, Nanocomposite, TGME, Compatibility&#x0D;

Combined Scanned Macro X-Ray Fluorescence and Reflectance Spectroscopy Mapping on Corroded Ancient Bronzes

Bronze is an alloy composed primarily of copper and tin and since its discovery is widespread in the whole world. This alloy can thus be found in many archaeological sites and its study can give information about the technology of production, the trading routes, or the warfare within a region. However, bronze artefacts can undergo severe alteration processes, and the formation of corrosion layers of different copper minerals can prevent the readability of the artefact or even destroy it, as in the case of the ‘bronze disease’. Their preservation is crucial for maintaining a connection to our cultural heritage. In this paper, we present the study of some corroded bronze artefacts found in different burying conditions. They have been analysed through a scanner system that combines two non-invasive techniques, macro XRF (MA-XRF) and visible, near infrared, short wave infrared (VIS-NIR-SWIR) reflectance, to unravel information about the metal and the patina composition, thickness, and distribution. As the corrosion of bronze depends on the burying conditions and the alloy composition, these data are of the utmost importance to understanding the alteration processes occurring in the archaeological site and to ensure the artefacts’ optimal preservation.

Mineralogical differences between seam and prism material in loess‐derived fragipans in western Kentucky

AbstractFragipan horizons are common diagnostic subsurface features typically identified by their dense, brittle nature under field conditions. Fragipan horizons are often hypothesized to contain various silicate bonding agents, including phyllosilicates, amorphous aluminosilicates/silica, and silica sorbed to iron oxyhydroxides. However, the association of silica (Si) with other minerals in these horizons remains uncertain. To fill this knowledge gap, we sampled the prism and seam material of four loess‐derived fragipan horizons in western Kentucky. We characterized and compared the clay mineral composition of the prism and seam material using X‐ray diffraction (XRD), selective extractions, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Fragipan prism and seam material exhibited a mixed clay mineralogy comprised of vermiculite, mixed layer minerals (hydroxyl‐interlayered vermiculite), illite, kaolinite, and quartz. We identified goethite in fragipan prisms in much greater quantities when compared to seam material, confirmed by both XRD and DRIFTS and corroborated by higher dithionite‐extractable iron in prisms. DRIFT spectra showed a peak near 3180 cm−1 assigned to OH‐stretching mode of goethite, which was prominent in prism materials. Goethite 110 XRD peak positions were negatively correlated to dithionite‐extractable aluminum (Al) and Si content of the prism material, which may suggest greater Si sorbed to the surfaces of Al‐substituted goethite. These results demonstrate the potential importance of Al‐substituted goethite in fragipan prisms and provide insight about possible associations with Si.

Alumina inhibits pyrite oxidative dissolution by regulating solid film passivation layer and S, Fe, and Al speciation transformation

The oxidation of pyrite results in the formation of a solid film passivation layer on its surface. This layer effectively hinders the direct interaction between H2O, O2, and the pyrite surface, thereby impeding the oxidation dissolution of pyrite. There are few studies on whether alumina (Al2O3), a common aluminum-containing oxide, affects the formation of a solid film passivation layer on the surface of pyrite and inhibits the oxidation dissolution of pyrite. This research investigates the impact of Al2O3 incorporation on the speciation transformation of S, Fe, and Al on the surface of pyrite during oxygen pyrite process. The oxidation of pyrite followed the “polysulfide-thiosulfate” complex oxidation pathway. When <1.5 g/L Al2O3 was introduced, it increase pyrite oxidation, whereas ≥1.5 g/L Al2O3 prevented pyrite oxidation. The process of Al2O3 dissolution results in the consumption of H+ and the subsequent release of Al3+. This, in turn, facilitates the hydrolysis of Fe3+ and Al3+ to generate a secondary mineral layer on the pyrite surface. As a result of the accumulation of S promotes the formation of polysulfide chemical (FeSn) or iron deficiency sulfide (Fe1-xS), resulting in the formation of a solid film passivation layer composed of sulfur film and secondary mineral layer. The results demonstrated that Al2O3 can promote the formation of a solid film passivation layer on the surface of pyrite, which has significant implications for controlling the oxidation dissolution process of pyrite and offers a new perspective for the source control of acid mine drainage.

Peptide Amphiphile‐Mediated Assembly and Fusion of Anisotropic Amorphous Particles for Enamel Remineralization

AbstractEnamel remineralization, which attempts to generate a mineral layer structurally similar to native enamel and restore its mechanical properties, remains a significant challenge. Here, rationally designed peptide amphiphile (PA) molecules bind to amorphous calcium phosphate (ACP) particles via electrostatic interactions, imparting anisotropic properties that drive PA‐modified ACP to form spindle‐shaped aggregates. Furthermore, some residual PA molecules may further regulate crystallization and facilitate the formation of well‐aligned hydroxyapatite bundles. Additionally, the involvement of PA can mediate the ordered deposition and fusion of ACP on the enamel surface, and construct the crystalline‐amorphous mineralization front with a continuous structure. This mineralization front ensures epitaxially oriented growth of enamel crystals and achieves a structurally ordered mineral layer similar to that of native enamel, while the mechanical performance is effectively restored. More significantly, the thickness of the newly formed mineral layer can be augmented through cyclic remineralization, benefitting the design of products intended for practical enamel repair.