Single Mineral Phase Research Articles

Global variability of the composition and temperature at the 410-km discontinuity from receiver function analysis of dense arrays

Seismic boundaries caused by phase transitions between olivine polymorphs in Earth's mantle provide thermal and compositional markers that inform mantle dynamics. Seismic studies of the mantle transition zone often use either global averaging with sparse arrays or regional sampling from a single dense array. The intermediate approach of this study utilizes many densely spaced seismic arrays distributed around the globe. We systematically compute teleseismic P-to-S receiver functions for each seismic array and invert for the 1-D seismic velocity structure of the mantle transition zone beneath each array to facilitate a comparison between densely sampled regions. We stack 3,600 receiver functions on average at 67 arrays in total. The stack is used in a probabilistic inversion to estimate the mantle transition zone interface depths and velocities beneath each array. We focus on the 410-km discontinuity (410) because it is a prominent seismic interface that is clearly linked to a single mineral phase transition between olivine and wadsleyite. The depths and velocity contrasts of the 410 are mapped to temperatures and compositions using mineral physics constraints. The depth of the 410 ranges from ∼405–440 km, which is consistent with a ∼360 K temperature range in a dry mantle and a ∼260 K temperature range in a wet mantle (2 wt. % water). The Vs contrast across the 410 ranges from ∼2.5–8 %, which is consistent with ∼20–70 vol. % olivine composition in a dry mantle and ∼25–80 vol. % in a wet mantle. The bulk composition of the upper mantle near the 410-km discontinuity is typically considered to be well-mixed because there is no thermodynamic impediment to convection at the olivine to wadsleyite phase transition. However, the wide range of inferred olivine content from our study suggests that there are large lateral variations in the bulk composition of the upper mantle near the 410-km discontinuity.

Carbonate Associated Sulfate Extraction Method Using Weakly Acidic Cation Exchange Resins

The sulfur (S) mass fraction of carbonate minerals can be used to reconstruct the environmental conditions and S sources at the time of precipitation. As S is present in a wide range of host materials, there is an urgent need to develop a method to extract S from a single mineral phase. We have developed a method to extract structurally substituted sulfate, termed carbonate‐associated sulfate (CAS), from geological and biogenic carbonate minerals using weakly acidic cation exchange resins. Two types of weakly acidic cation exchange resin (methacrylic acid and acrylic acid types) were tested to minimise the blank S contents and decompose carbonate. After repeated cleaning of the resins with high‐purity water or HCl, the blank S contents were reduced to < 0.1 μg, which is < 0.1% of the CAS in the samples. The cleaned resin was used to dissolve 10 and 25 mg of the JCp‐1 carbonate certified reference material (CRM; Japanese National Institute of Advanced Industrial Science and Technology, AIST). Samples and resin were added to 8 ml of high‐purity water at resin/sample ratios of 2, 5, 10 and 20, set on a shaking table, and reacted. The supernatant solutions were sampled sequentially from 0.5 h to 87 h after the start of experiments. The results show that the optimal conditions for decomposing 10 mg of carbonate is a resin/sample ratio of ≥ 10 with a reaction time of ≥ 40 h. Carbonate‐associated S mass fractions were measured for six geological and biogenic carbonate CRMs. The coefficient of variation in carbonate‐associated S mass fractions was ≤ 7%, regardless of the type of resins used. The mass fractions determined with this method recover 74–94% of the total S mass fractions reported in previous studies, suggesting that this method dissolved carbonate, and did not leach other S‐bearing fractions that are not resistant to weak acids. Another benefit of this method is that the decomposed solution can be introduced directly into the ion chromatograph, allowing for more sensitive analyses. We emphasise that this method can also be used for S isotopic measurements, as S contamination from other S‐bearing mineral phases is low.

An investigation of mineral floatability versus mineral surface exposure and hydrophobicity by high-resolution X-ray microcomputed tomography, film flotation, contact angles, and modeling

Determination of mineral floatability versus mineral surface exposure and hydrophobicity has been challenging because of significant deviations of flotation model assumptions for real mineral surfaces and the unavailability of suitable research tools. Here, we report a successful application of combined advanced experimental techniques and modeling to determine mineral floatability versus mineral surface exposure and hydrophobicity. Specifically, high-resolution X-ray microcomputed tomography (HRXMT) was used to determine the surface exposure of composite mineral particles of quartz and chalcopyrite and compared it with the mineral floatability obtained by film flotation experiments and the contact angle (CA) of the mineral particles. The surface exposure was obtained from the HRXMT images using in-house software. Cassie's theory was applied to estimate the CA of composite particles from the CAs on single mineral phases. The mineral floatability was described by extending the new theory on max adhesion force (tenacity) that holds the particles attached to the bubble surface. The comparison shows a good agreement between the tenacity, surface tension, and the CA calculated from the surface exposure data together with the CA on single mineral phases. This is the first work that quantifies the effect of surface exposure on the floatability of composite particles and can be applied to predict the flotation performance of the composite particles in the mineral processing industry.

Low-cost zeolitic carriers for delivery of hydroxychloroquine immunomodulatory agent with antiviral activity

The coronavirus pandemic prompted scientists to look for active pharmaceutical ingredients that could be effective in treating COVID-19. One of them was hydroxychloroquine, an antimalarial and immunomodulatory agent exhibiting antiviral activity. The anchoring of this drug on porous carriers enables control of its delivery to a specific place in the body, and thus increases bioavailability. In this work, we developed low-cost zeolitic platforms for hydroxychloroquine. The waste solution generated during zeolite production from fly ashes was used in the synthesis of Na-A and Na-X carriers at laboratory and technical scale. The materials were characterized by high purity and single mineral phase composition. The surface charge of zeolites varied from negative at pH 5.8, and 7.2, to positive at pH 1.2. All samples indicated good sorption ability towards hydroxychloroquine. The mechanism of drug adsorption was based on electrostatic interactions and followed the Freundlich model. Zeolitic carriers modified the hydroxychloroquine release profiles at conditions mimicking the pH of body fluids. The mode of drug liberation was affected by particle size distributions, morphological forms, and chemical compositions of zeolites. The most hydroxychloroquine controlled release at pH 5.8 for the Na-X material was noted, which indicates that it can enhance the drug therapeutic efficacy.

Synthesis of Magnetite Nanoparticles through a Lab-On-Chip Device.

Magnetite nanoparticles (MNPs) represent one of the most intensively studied types of iron oxide nanoparticles in various fields, including biomedicine, pharmaceutics, bioengineering, and industry. Since their properties in terms of size, shape, and surface charge significantly affects their efficiency towards the envisaged application, it is fundamentally important to develop a new synthesis route that allows for the control and modulation of the nanoparticle features. In this context, the aim of the present study was to develop a new method for the synthesis of MNPs. Specifically, a microfluidic lab-on-chip (LoC) device was used to obtain MNPs with controlled properties. The study investigated the influence of iron precursor solution concentration and flowed onto the final properties of the nanomaterials. The synthesized MNPs were characterized in terms of size, morphology, structure, composition, and stability. Results proved the formation of magnetite as a single mineral phase. Moreover, the uniform spherical shape and narrow size distribution were demonstrated. Optimal characteristics regarding MNPs crystallinity, uniformity, and thermal stability were obtained at higher concentrations and lower flows. In this manner, the potential of the LoC device is a promising tool for the synthesis of nanomaterials by ensuring the necessary uniformity for all final applications.

Nano-Hydroxyapatite vs. Xenografts: Synthesis, Characterization, and In Vitro Behavior.

This research focused on the synthesis of apatite, starting from a natural biogenic calcium source (egg-shells) and its chemical and morpho-structural characterization in comparison with two commercial xenografts used as a bone substitute in dentistry. The synthesis route for the hydroxyapatite powder was the microwave-assisted hydrothermal technique, starting from annealed egg-shells as the precursor for lime and di-base ammonium phosphate as the phosphate precursor. The powders were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM), X-ray fluorescence spectroscopy (XRF), and cytotoxicity assay in contact with amniotic fluid stem cell (AFSC) cultures. Compositional and structural similarities or differences between the powder synthesized from egg-shells (HA1) and the two commercial xenograft powders—Bio-Oss®, totally deproteinized cortical bovine bone, and Gen-Os®, partially deproteinized porcine bone—were revealed. The HA1 specimen presented a single mineral phase as polycrystalline apatite with a high crystallinity (Xc 0.92), a crystallite size of 43.73 nm, preferential growth under the c axes (002) direction, where it mineralizes in bone, a nano-rod particle morphology, and average lengths up to 77.29 nm and diameters up to 21.74 nm. The surface of the HA1 nanoparticles and internal mesopores (mean size of 3.3 ± 1.6 nm), acquired from high-pressure hydrothermal maturation, along with the precursor’s nature, could be responsible for the improved biocompatibility, biomolecule adhesion, and osteoconductive abilities in bone substitute applications. The cytotoxicity assay showed a better AFSC cell viability for HA1 powder than the commercial xenografts did, similar oxidative stress to the control sample, and improved results compared with Gen-Os. The presented preliminary biocompatibility results are promising for bone tissue regeneration applications of HA1, and the study will continue with further tests on osteoblast differentiation and mineralization.

Classification, segmentation and correlation of zoned minerals

Minerals exhibit compositional zoning patterns that can be related to changes in the environment in which they grew. Using statistical methods that have been designed to segment optical images, we have developed a procedure to segment zoned crystals using elemental maps. For a single mineral phase, compositional zones in individual crystals are correlated between multiple crystals. This allows us to quantify the complexity and variability of chemical zoning between different geological samples. Specifically, we employ a simple linear iterative clustering algorithm, which splits the chemical maps into spatially constrained regions of similar chemistry. The result is a texturally segmented crystal, akin to what would be identified by the human eye. To aid the segmentation and correlation of zones, we also introduce a new method to classify multiple mineral phases within a single thin section. This is based on a finite mixture model approach, which proves very effective in removing mixed pixels that will only introduce noise into the segmentation. We provide an example using the mineral phase plagioclase. Using two contemporaneous samples from an eruptive unit on the island of St. Kitts (Eastern Caribbean) we show that a volcanic bomb (~10 cm) and a scoria clast (~2 cm) have similar rim compositions but distinctly different core compositions. Our methodology will enable a statistical characterization of 2D complexity of crystals in a variety of different geo-scientific disciplines. This will allow the genesis of different mineral phases to be directly compared.

Thermal emission measurements of ordinary chondrite mineral analogs in a simulated asteroid environment: 1. Constituent mineral phases

Telescopic surveys suggest that S-type asteroids are the dominant small body type in the near-Earth object population and are among the most abundant in the inner main asteroid belt. Given the link between S-type asteroids and the ordinary chondrites, regoliths of ordinary chondrite mineralogy may represent the most common regolith type on small bodies in these populations, and therefore it is important to understand the thermal emission properties of ordinary chondrite mineral analogs radiating into asteroid-like environments. Thermal infrared spectra of particulate surfaces in airless environments are substantially modified due to near-surface thermal gradients formed between the immediate surface undergoing radiative cooling and underlying materials that are warmed by the absorption of solar radiation. To advance our understanding of how the thermal emission properties of materials relevant to ordinary chondrite composition may be modified in an airless environment, we analyze a suite of analogous single mineral phases in a simulated asteroid surface environment. A companion paper presents and discusses analyses of modal mixtures of these minerals designed to match modal abundances of ordinary chondrites as reported in the literature. We probe the thermal emission of these materials by investigating relationships between their sample temperatures, emissivity spectra, brightness temperatures, and the environmental and experimental conditions. We focus attention on the radiance spectra of the samples as derived by two data reduction methods and their corresponding brightness temperature spectra to infer the intensity of near-surface thermal gradients formed in the samples. We demonstrate that the Christiansen feature position is sensitive to the sample cup temperature with data collected in a simulated asteroid environment under constant illumination condition. Through the analysis of particulate samples of three particle size ranges (<25 μm, 25–125 μm, and 125–250 μm) at ambient and cold, vacuum conditions, we demonstrate that thermal gradients form as a result of the physical, environmental, and optical properties of the target surface. Using temperature variations observed in high spectral resolution brightness temperature spectra as a proxy for the near-surface thermal gradients, we observe relationships between the intensity of the thermal gradient and the sample particle size. Modifications of iron metal spectra due to the changing environmental conditions are examined and compared with the silicate data. Implications for the measurement of thermal infrared spectra of metal-bearing planetary materials, such as the ordinary chondrites, are discussed.

Influence of the Precursor and the Temperature of Synthesis on the Structure of Saponite

AbstractSeveral procedures for hydrothermal synthesis of saponite can be found in the literature. They differ in terms of the preparation conditions of the precursor and of the synthesis temperature. The objective of the present study was to investigate how these two parameters influence the structure of the final synthesis product. The precursor was prepared from Mg(NO3)2, Al(NO3)3, and Na4SiO4 in three different ways: as a gel, a dried gel, and a calcined gel. The influence of the synthesis temperature on the structure of saponite was investigated in the range 90–200°C. The results showed that the use of a calcined precursor yielded a single mineral phase, saponite, with up to 90% aluminum in tetrahedral configuration. In comparison, the use of a gel precursor resulted in a product with only 60% aluminum in the tetrahedral configuration. The synthesis temperature had no significant effect on the saponite structure. The reported synthesis method showed the possibility of obtaining saponite with superior characteristics, in terms of crystallinity, surface acidity, and thermal stability compared to the natural mineral, even at 90°C, and thus with greater potential for industrial application.

A Bayesian approach to the deconvolution of 40Ar/39Ar data from mineral mixtures

40Ar/39Ar geochronology is a powerful technique for dating geological events and processes on timescales from hundreds to billions of years. Many 40Ar/39Ar datasets are collected from analysis of single mineral phases or phenocryst-free groundmass that cooled rapidly following a volcanic eruption, which can allow for straightforward interpretation of 40Ar/39Ar age spectra. However, 40Ar/39Ar age spectra from mixtures of multiple minerals and/or multiple age components are often complex. In such situations, interpretations commonly used for single mineral phases are inappropriate and will result in geologically spurious conclusions. Here, we present a Bayesian method for the analysis and interpretation of 40Ar/39Ar step-heating spectra that result from mixing of multiple components, where a component is defined by both its age and mineral composition. We test the efficacy of this Bayesian approach using a suite of case studies. Two of these case studies utilize 40Ar/39Ar data from laboratory-prepared mixtures, which we use to explore how the composition, age, and number of components in a mixture, as well as our prior knowledge of these parameters, influence the model results. We also present an application-based case study in which we use plausible compositions and ages from a past Mars landing site to generate a synthetic 40Ar/39Ar dataset, which we then deconvolve using our Bayesian approach. We discuss modifications to our method that could improve the model's precision and outline geologic applications of our Bayesian approach in terrestrial and extraterrestrial settings that would permit the extraction of a greater amount of temporal information.

Geochronologic constraints on deformation and metasomatism along an exhumed mylonitic shear zone using apatite U-Pb, geochemistry, and microtextural analysis

Directly dating and characterizing deformation and metasomatism in fault zones is critical to understanding fault zone processes and lithospheric evolution. Integrated apatite U-Pb geo-thermochronometry, geochemistry, and microtextural analysis has potential to directly date and characterize deformation and fluid-rock interactions in shear zones using a single mineral phase. Integrated apatite U-Pb, microtextural, and trace and rare earth element results from an exhumed mylonitic shear zone, the Main Mylonitic Band in the Northern Pyrenees, constrain timing of deformation and metasomatism along the shear zone as Early Cretaceous, synchronous with ductile deformation and exhumation of middle-lower crustal gneisses in the footwall, and significant mineralization and metasomatism in the brittle hanging wall. Samples from the hanging wall preserve magmatic apatite U-Pb crystallization ages that overlap with zircon and monazite U-Pb ages of ∼300 Ma, granitic geochemical trends, and primary magmatic growth zoning. Footwall samples below the MMB record dynamic recrystallization of apatite associated with mylonitization and exhumation of the gneisses in the Early Cretaceous. Apatite along the MMB record partial recrystallization via dissolution-reprecipitation associated with shearing and circulation of deeply sourced fluids along the shear zone evident by mixed ages (300-100 Ma), geochemical signatures enriched in light rare earth elements, and patchy microtextures. The MMB likely acted as a conduit for deeply sourced fluids that affected the brittle-ductile transition, strain localization, and fluid pathways through the continental crust. This study demonstrates that the integration of apatite U-Pb geo-thermochronology, geochemistry, and microtextural analysis is a powerful approach to dating deformation and metasomatism, characterizing grain scale deformation and (re)crystallization processes, and geochemically characterizing fluid-rock interactions in exhumed middle crustal shear zones.

Chemical, mineralogical and petrological characterization of Gyaza iron ore deposit, Katsina State, Nigeria

Chemical, mineralogical and petrological characterization of Gyaza iron ore deposit, Katsina State, Nigeria was carried out. The ore sample was sourced from Gyaza village, Kankiya Local Government Areas of Katsina State and comminuted using laboratory jaw crusher and pulverizing machines respectively. The comminuted sample was analyzed using XRF, XRD, SEM and OPM. The XRF result revealed that the ore contained 0.17%P, 0.02%K, 0.23%Ca, 0.11%Mn, 36.17%Fe, 0.08%Ba, 0.18%Mg, 1.10%Al and 17.21%Si. The XRD result revealed that the complex mineral phases of the ore are Aluminum-Silicate-Hydroxide-Hydrate (Al2Si2O5(OH)4.2H2O), Chrysotile (Mg3[Si2-xO5](OH)4-4x), Magnesium-Aluminum-Silicate-Hydroxide-Hydrate ((Mg,Al)9 (Si,Al)8O20 (OH)10.4H2O), Sodium-Calcium-Magnesium-Aluminum-Silicate (NaCa2Mg5AlSi7O22(OH)2), Sodium-Iron-Silicate-hydroxide ((Na,Ca) 2 (Fe,Mn)Fe2 (Si,Al)8O22 (OH)), Orthoclase (KAlSi3O8) and Sodium-Calcium-Iron-Aluminum-Silicate-Hydrate (NaCa2Fe4AlSi6Al2O22(OH)2). And the single mineral phases are Quartz (SiO2), Hematite (Fe2O3) and Goethite (Fe2O3.H2O) which are also the major minerals phases. The SEM and petrological results revealed that the ore matrix is an assemblage of inter-layered different minerals crystals with different shapes, sizes and angles of orientations and separated by grain boundaries. http://dx.doi.org/10.4314/njt.v38i3.17

Determination of the Mineral Composition of the Lake Bottom Sediments by X-Ray Diffraction Method and Physico-Chemical Modelling

The paper reports comparison of three approaches to define the contents of minerals and mineral groups in the carbonate-silicate lake bottom sediments. The two approaches are based on the method of X-ray powder diffraction. The first one treats with the Rietveld Method in the software DIFFRAC Plus diffractometer D8 Advance (PDF-2 database). The second one uses the method of reference intensities (corundum ratios) and optimization of the model powder patterns from the X-ray phase standards of PDF-2 database and equations of the element balance with regularization of the least square functional. The third approach of physic-chemical modeling selects probable single mineral and multi-component phases through modelling the sold solutions, and it uses the data on the element composition obtained by XRF technique, as well as the data of X-ray diffraction on the qualitative mineral composition. Thirty samples of bottom sediment cores taken in the Zun-Torey Lake in East Siberia were analyzed by the three approaches described herein. The contents of mineral groups (feldspars, quartz, clay minerals and carbonates) varied within the range 10-40 mass %. The discrepancies between obtained results show the standard deviation ranging from 2 to 9 mass %. A relative standard deviation commonly provides the value below 30 %, so such determinations could be considered quantitative ones. With regard to the acquired data, it is hard to prefer this or that approach. Available data was employed to assess the error of X-ray phase powder analysis in measuring the abundance of mineral groups in the carbonate-silicate sedimentary rocks in the absence of reference materials to compare with certified mineral composition

Age and rate of weathering determined using uranium-series isotopes: Testing various approaches

Abstract The development of weathering profiles shapes Earth’s surface and regulates its climate via chemical weathering. Hence, it is essential to be able to determine the age of weathering profiles and quantify how fast they form. Uranium-series isotopes allow for such quantification. However, isotope compositions are generally measured in bulk regolith, which represents a complex mixture of mineral and organic phases of different origins that can impact the reliability of the information derived from U-series isotopes. Thus, in this study, we assess whether sequential extraction and mineral separation could provide more reliable estimates of weathering ages and rates. We focus on a granitic profile developed under temperate climate in southeastern Australia, a tectonically quiescent environment. Regolith production rates have been independently estimated in the region using cosmogenic isotopes. As expected, the mineralogy and geochemistry of the bulk regolith show that biotite and feldspar are the main phases lost during weathering, progressively replaced by clay minerals. There is no evidence for significant input of element from external sources, such as via aerosol deposition. While sequential extraction does not seem to affect major mineral phases and element concentrations, it is suspected of producing artificial radioactive disequilibrium. Biotite separates show very large accumulation of U and Th, which increases with decreasing depth. Regolith production rates and mineral dissolution rates calculated with weathering rates estimated using the bulk saprolite and quartz separate compositions yield values comparable to independent estimates. Conversely, weathering ages derived from the compositions of saprolite leached experimentally or biotite separates underestimate regolith production rates and mineral dissolution rates. Thus, sequential extraction or biotite separation are not recommended methods to derive reliable rates of regolith production and mineral dissolution. Despite the potential complexity of the composition of bulk regolith, the use of regolith without any pre-treatment seems to yield satisfying estimates of regolith production and mineral dissolution rates. The composition of quartz separates yields rates similar to those derived from bulk compositions. This provides an alternative method, potentially allowing reliable results to be obtained from a single mineral phase rather than a complex mixture of weathering products.

PHASE COMPOSITION, THERMAL BEHAVIOR AND MAGNETIC PROPERTIES OF ZINC- AND NICKEL-BEARING POWDERS FORMED ON THE STEEL SURFACE IN THE OPEN-AIR SYSTEM

The nanosized powders formed on the steel surface contacting with zinc and nickel inorganic water salt solutions have been studied using an X-ray diffraction method, thermal analytical measurements (TG/DTG, DTA,) scanning electron microscopy, and magnetometry. It was shown that the formation of a single mineral phase of a non-stoichiometric spinel ferrite when zinc and nickel nitrate solutions were used as the dispersion medium, but in the presence of chloride-containing salts three mineral phases (spinel ferrite, lepidocrocite, and goethite) were determined in the phase composition of the surface powders. When sulfate solutions were chosen as the dispersion medium the mixed hydroxysulfate layered double hydroxides (LDHs) simultaneously appeared among other components of the powders. Due to cation exchange between Fe 2+ and Zn 2+ or Ni 2+ the mixed LDH structures achieved stability against further oxidation and thermal transformation. Hence, the presence of mixed LDHs in the phase composition of the powders significantly complicates the obtaining of homogenous superparamagnetic 3 d -metal doped spinel ferrite and iron oxide powders.

Fe isotope behaviours during sulfide-dominated skarn-type mineralisation

Fe isotope compositions of mineral separates and bulk samples from Dongguashan and Fenghuangshan skarn type Cu–Fe deposits in Tongling District, Middle–Lower Yangtze Valley Cu–Fe–Au–Mo polymetallic belt have been investigated. Differences in δ57Fe values exist in co-precipitated bornite–chalcopyrite and pyrite–chalcopyrite mineral pairs. The bornite is enriched in light iron isotopes relative to coexisting chalcopyrite, whereas pyrite samples show a tendency of heavy isotopes enrichment relative to chalcopyrite. Moreover, the δ57Fe values of endoskarn and the earliest formed Fe-mineral phase magnetite of the three deposits investigated in Tongling district are consistently lower relative to ore-related igneous rocks, suggesting Fe isotopic fractionation occurs during fluid exsolution and exsolved fluid is enriched in light Fe isotopes relative to the stock. Furthermore, spatial and temporal variations in δ57Fe values within single mineral phases are observed, suggesting iron isotopic fractionation occurs between mineral and fluid phases as a result of precipitation of Fe-bearing minerals during fluid evolution. Overall, according to Fe isotope compositions of three representative skarn deposits formed under the same geological setting in Tongling district, this study indicates that Fe isotopes have the potential to unraveling ore-forming processes, as well as constraining the metal sources of skarn deposits. Combining with results of previous studies, a protocol for using Fe isotopes to trace skarn-type metallogeny is proposed.

Arsenite Removal from Aqueous Solution using Mixed Mineral Systems Injected with Iron Sulfide under Sulfidic- Anoxic conditions 1: Reactivity and Removal Kinetics

The reactivity and removal kinetics of arsenite treated with single and mixed mineral systems of kaolinite, montmorillonite and goethite injected with iron sulfide under sulfidic- anoxic conditions has been investigated. Using empirical models derived from Freundlich isotherm model, injection of sulfidic-anoxic solution of iron sulfide onto the mixed mineral systems enhanced proton coefficient of all single minerals. Differences in sorption kinetics between the single and mixed mineral phases may be attributed to different types of reactive sites on the single and mixed mineral systems Except for iron sulfide, kinetic studies demonstrated three phase reactions attributed to outer sphere complexation, inner sphere complexation and intra-particle diffusion. Injection of sulfidic-anoxic solution of iron sulfide could not change the three phase reaction trend.

Sorption of Eu(III) on Granite: EPMA, LA–ICP–MS, Batch and Modeling Studies

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

Thermally induced alterations of minerals during measurements of the temperature dependence of magnetic susceptibility: a case study from the hydrothermally altered Soultz-sous-Forêts granite, France

Identification of magnetic minerals using the temperature dependence of magnetic susceptibility in low field (κ–T) combined with optical microscopy, microprobe, X-ray diffraction, and chemical analysis provided new constraints on the alteration of Fe-bearing minerals of the magnetite-bearing Soultz-sous-Forets granite from the EPS-1 borehole (upper Rhine Graben, France). While relatively fresh granite shows largely reversible κ–T curves typical of magnetite, the altered granite revealed a wide variety of irreversible heating and cooling curves, which allowed an assignment to different alteration stages under specific geochemical conditions. Though paramagnetic minerals like Fe-bearing carbonates, pyrite, or antiferromagnetic hematite could not be detected according to their Curie or Neel temperature, they were identified due to reactions to new ferrimagnetic phases during the heating/cooling experiments at specific temperatures. Mineral reactions were proved by measurements of the single mineral phases hematite, Fe-carbonates, and illite. Our mineralogical results combined with the thermomagnetic measurements imply that first faulting of the granite occurred already during cooling of the magma, which caused a first magnetite oxidation event. During uplift of the granitic body and exposure to a paleo-erosion surface, strongly acidic fluids, emerged from pyrite oxidation, caused a decomposition of Fe-bearing minerals like martite (hematite derived from magnetite oxidation) and Fe-carbonates and an ongoing transformation of magnetite to martite. Subsequently, precipitation of fine-grained hematite was restricted only to the upper part of the pluton. In the deeper part of the borehole, pyrite was preserved from oxidation. In an active fault, zone martite was reduced back to magnetite, which can be explained with the occurrence of organic matter transported by fluids.

The Application of the Coal Grain Analysis Method to Coal Liberation Studies

Emerging coal markets such as the use of coal for conversion to liquid fuels and its use in fuels cells and as coal water slurries in diesel engines require coal products with different coal quality specifications than those applicable to traditional coal markets of coke making and conventional power generation. As well as quantifying coals in terms of their chemical and physical properties, detailed knowledge of the mineral inclusions within the coal particles is required to identify coals that are suited to economically produce the low-ash value coals required for these markets. Hence, it is necessary to understand the associations of the minerals and macerals in individual particles as these give a particular coal not only its chemical attributes and utilization performance but also its washability (density distribution) and contribute to its surface chemistry characteristics. These attributes pinpoint the coals that are suited to beneficiation techniques that can be employed to produce economic amounts of low-ash value products for these new markets. After mining and processing, some particles can consist of essentially pure components of a single maceral or mineral phase whilst others are composite particles that are comprised of varying amounts of macerals and minerals. The proportion of particles that are present as pure components or as composites will be a function of the characteristics of the coal and the particle size. In general, it is considered that size reduction will result in liberation and hence increased yield. The amount of liberation that occurs during crushing or grinding a coal is however coal specific. Particle characterization information provided by an optical microscopic-imaging method, Coal Grain Analysis, was used to identify coals that might benefit from additional crushing to improve recovery of clean coal by new density separation techniques and by flotation. As expected, the results of these studies suggest that the degree of liberation that is obtained is coal specific, and, hence, yield improvements are also coal specific. Hence a quantitative method of investigating this issue is required.