Silicate Samples Research Articles

In-Depth Method Investigation for Determination of Boron in Silicate Samples Using an Improved Boron-Mannitol Complex Digestion Method by Inductively Coupled Plasma Mass Spectrometry.

In this paper, a boron-mannitol complex wet acid digestion method proposed for the accurate determination of boron in silicate samples by inductively coupled plasma mass spectrometry (ICP-MS) was investigated in detail for the first time. With the addition of 50 μL of mannitol (2% wt.) into the mixture of 0.6 mL of concentrated HF and 30 μL of concentrated HNO3, the 50 mg of silicate sample was effectively decomposed after being heated overnight with optional pre-ultrasonic treatment. Following fluoride formation prevention by 8% HNO3 (wt.) and fluoride decomposition using 6% HCl (wt.), the samples were fluxed in 2.0 mL of 40% HNO3 (wt.) for 4 h and aged overnight. By diluting 1000-fold using 2% HNO3 (wt.) solution, the samples were directly quantified by an ICP-MS, showing boron recoveries of the standard materials including diabase W-2, basalt JB-2a, and rhyolite JR-2 in the range of 95.5-105.5% (n = 5). For this wet acid method, it was found that the contents of boron had no obvious difference under digestion temperatures of 65, 100, and 140 °C. It was also found that the ICP-MS quantification accuracy deteriorated at the mass of 11B when boron content was about 7250 ng yielding positive bias with average recoveries of 115.5-119.8% (n = 5), while the determination results remained unaffected at the mass of 10B. Furthermore, the digestion efficiency of boron by laboratory high-pressure closed digestion method was assessed. The boron recoveries with samples treated by the high-pressure closed digestion method were found to vary within 49.5-98.0% (n = 5) and even lowered down to 31.1% when skipping pressure relief procedure. The long-term quantification stability study showed that the boron content generally declined in one month for the high-pressure closed digestion method and exhibited no significant changes for the proposed method. By applying such an improved boron-mannitol complex digestion method, the boron concentration in the studied silicate standard materials were accurately determined, providing critical data for further boron isotope analyses and associated geochemical studies. This in-depth method investigation for silicate boron determination demonstrates the feasibility of this boron-mannitol complex strategy under a wide digestion temperature of 65-140 °C, and also sheds light on the extensive applications of boron as a geological tracer.

The influence of compositional variability of dimension stone residues on the properties of rustic porous ceramic tiles

This study analyzed how the compositional variability of dimension stone residues influences the characteristics of rustic porous ceramic tiles. The specimens were prepared by adding 20 wt% of dimension stone residue to the clay and sintered at 1000 °C for 1 h. The testing assays performed were physical properties and structural analysis through scanning electron microscopy. The results indicate that water absorption was lower (~9% to 14%) in samples containing silicate residues compared to carbonate residues (~16%). Apparent porosity of ~21% to 25% and shrinkage of 0.5% to 1.6% were measured in silicate samples while higher apparent porosity of ~30% and expansion of -0.04% were found in carbonate samples. Flexural strength and modulus of rupture were similar, ~16 MPa and ~330 N, respectively, for both sample sets. The samples containing silicate residues whose SiO2 content was between 48% and 58% and the sum of alkaline and alkaline earth oxides was less than 18% were suitable for manufacturing rustic porous ceramic tile, while residues with high SiO2 or carbonate contents impaired the properties of the ceramic bodies. Therefore, it is recommended that the dimension stone residues intended for use in ceramic tiles be previously separated according to chemical and mineralogical characteristics.

Influence of Supercritical Water on the Composition and Distribution of Microelements in Resins, Asphaltenes, Kerogens, and Rocks of Tatarstan Domanik Deposits of Different Lithological Types

A comparative study of changes in the microelemental composition and distribution in resins, asphaltenes, and kerogens from Tatarstan Domanik rocks, occurring under the action of supercritical water (SCW) at 374°С and a pressure of 22–24 MPa, was made. The samples studied belong to different lithological types; they were taken from carbonate–siliceous deposits of the Romashkino and Tavel oilfields and from carbonate deposits of the Bavly oilfield. The specific features of distribution of different microelements (MEs) in rocks and rock organic matter (OM) components were revealed by inductively coupled plasma mass spectrometry (ICP-MS). The major MEs are Fe > Ti > Ni > Zn > V > Cr > Cu with the concentrations from 100 to 8600 ppm. The total ME content of rocks from these deposits is 1.14, 0.23, and 0.38%, respectively. The ME content of resins and asphaltenes does not exceed 0.3 and 2%, respectively. The highest ME content, 8%, is observed in kerogens. The carbonate–siliceous rocks from different deposits with Сorg 7.07 and 1.90% differ from the carbonate rock with low Сorg (0.33%) in that the ME concentration in them is maximal. On the other hand, the ME content of resins and asphaltenes from the carbonate rocks is higher compared to the carbonate–siliceous rock samples. The concentrations of Fe, Cu, As, Se, Pb, and Bi in kerogens of all the types decrease under the action of SCW. In the transformed resins and asphaltenes from carbonate–siliceous rocks, the V and Ni concentrations appreciably decrease, whereas in kerogens their concentrations do not change noticeably. The demetalation processes lead to the ME redistribution between the OM components and mineral surface of the rocks.

Neural network for determining an asteroid mineral composition from reflectance spectra

Context.Chemical and mineral compositions of asteroids reflect the formation and history of our Solar System. This knowledge is also important for planetary defence and in-space resource utilisation. In the next years, space missions will generate extensive spectral datasets from asteroids or planets with spectra that will need to be processed in real time.Aims.We aim to develop a fast and robust neural-network-based method for deriving the mineral modal and chemical compositions of silicate materials from their visible and near-infrared spectra. The method should be able to process raw spectra without significant pre-processing.Methods.We designed a convolutional neural network with two hidden layers for the analysis of the spectra, and trained it using labelled reflectance spectra. For the training, we used a dataset that consisted of reflectance spectra of real silicate samples stored in the RELAB and C-Tape databases, namely olivine, orthopyroxene, clinopyroxene, their mixtures, and olivine-pyroxene-rich meteorites.Results.We used the model on two datasets. First, we evaluated the model reliability on a test dataset where we compared the model classification with known compositional reference values. The individual classification results are mostly within 10 percentage-point intervals around the correct values. Second, we classified the reflectance spectra of S-complex (Q-type and V-type, also including A-type) asteroids with known Bus–DeMeo taxonomy classes. The predicted mineral chemical composition of S-type and Q-type asteroids agree with the chemical composition of ordinary chondrites. The modal abundances of V-type and A-type asteroids show a dominant contribution of orthopyroxene and olivine, respectively. Additionally, our predictions of the mineral modal composition of S-type and Q-type asteroids show an apparent depletion of olivine related to the attenuation of its diagnostic absorptions with space weathering. This trend is consistent with previous results of the slower pyroxene response to space weathering relative to olivine.Conclusions.The neural network trained with real silicate samples and their mixtures is applicable for a quantitative mineral evaluation of spectra of asteroids that are rich in dry silicates. The modal abundances and mineral chemistry of common silicates (olivine and pyroxene) can be derived with an accuracy better than 10 percentage points. The classification is fast and has a relatively small computer-memory footprint. Therefore, our code is suitable for processing large spectral datasets in real time.

Geochemistry and depositional settings of Paleozoic cherts from Western Bulgaria: preliminary results

Paleozoic (Silurian and Devonian) cherts from Western Bulgaria occur in three tectonic units: Svoge, Lyubash-Golo Bardo and Morava. The SiO2 content in these rocks varies from 76.06% to 96.02%. The silica source and depositional settings of the cherts have been interpreted based on the received geochemical major element data. The calculated Si/(Si+Fe+Al+Ca) ratio and Al–Fe–Mn diagram plotting at non-hydrothermal field suggest that most of silica in the cherts is biogenic or both biogenic and terrigenous in origin. On the other hand, all studied siliceous samples plot into the field of the continental margin sediment environments on the Fe2O3/TiO2 vs. Al2O3/(Al2O3+Fe2O3) diagram. The calculated MnO/TiO2 ratio also indicates deposition in continental shelf or slope environments.

Light-induced fading of the photostimulated luminescence and thermoluminescence for irradiated silicate samples

By introducing standard physical methods for the detection of irradiated herbs and spices by photostimulated luminescence and thermoluminescence, measurements of different irradiated samples have been undertaken and an analysis of the results has been done. Since luminescence may occur under natural and artificial light stimulation on which herbs and spices may be exposed during storage, leading to false-negative results and disabling their proper identification, studied samples have been kept under different light conditions for different periods. The optical bleaching of the photostimulated luminescence and thermoluminescence signal has been detected in all cases. The strong influence of light, natural and artificial, on the photostimulated luminescence signal has been determined.

Study on the distribution and connectivity of organic matter pores in Longmaxi shale based on 2D and 3D FIB‐SEM

AbstractKnowledge of shale pore structure characteristics is crucial to understand gas storage and seepage mechanisms. Organic matter (OM) pores are considered the most important pore type in shale, and one of the currently significant research questions focuses on the spatial distribution and connectivity of OM pores. To answer this question, typical OM‐rich siliceous shale samples from the Lower Silurian Longmaxi Formation were comprehensively investigated using focused ion beam scanning electron microscopy. A three‐dimensional model of the OM‐rich region of interest was segmented and reconstructed based on numerous two‐dimensional slices. The types of OM were found to control the development of organic pores, and OM pores including honeycomb‐shaped pores, spongy‐shaped pores, and slit‐like irregular pores are mainly formed in the pyrobitumen. The pore structure parameters of the OM‐rich ROI revealed that the pore size distribution of honeycomb‐shaped OM pores formed in the pyrobitumen was mainly distributed in the range of 10–50 and 80–100 nm, while the throat equivalent diameter distribution demonstrated a unimodal curve with the main peak located at approximately 30 nm. Pore connectivity analysis further indicated that pyrobitumen also contained several isolated nano‐pores, and pores with diameters smaller than 40 nm were poorly connected. Furthermore, permeability simulation revealed clear discrepancies in different directions owing to the heterogeneity of the OM pores. These findings provide experimental evidence for the assessment of shale gas resources and their development potential.

Adsorption-Induced Fluorescence of Pseudoisocyanine Monomers in Systems with Layered Silicates

Interaction of organic dyes with layered silicates can cause various changes in dye properties, such as metachromasia (color change), fluorescence quenching, resonance energy transfer, or even fluorescence enhancement. These phenomena are caused by the molecular aggregation or adsorption of dye molecules on silicate particles. The present work studied the photophysical properties of pseudoisocyanine (PIC) in colloidal dispersions of five samples of layered silicates (smectites) at variable PIC/smectite loadings. The silicates of variable composition and layer charge included one synthetic saponite, one synthetic hectorite, two synthetic Laponites, and one montmorillonite. Chemometric analysis of the absorption spectra revealed the formation of four spectral species: monomers and three types of molecular aggregates exhibiting light absorption in both H- and J-band regions. In addition, the samples of hybrid systems with silicates of lower layer charge under the condition of the lowest PIC/silicate ratio (0.01 mmol g–1) exhibited strong fluorescence surpassing that of J-aggregates. The luminescent species achieving quantum yields of about 50% were assigned to the adsorbed PIC monomers, a phenomenon that has never been observed for this dye. Theoretical calculations found that in water solution bending of the molecule supports nonradiative deactivation of the excited state of the free molecule. Adsorption of PIC molecules on the surface of silicate particles caused the change of the dihedral angle between pyridine subunits, which hinders the nonradiative deactivation channel and favors emission. Fluorescence from adsorbed monomers exhibited a maximum at ≈535 nm, which is at significantly lower wavelengths with respect to the J-aggregates emitting at ≈570 nm and thus cannot be related to dye aggregation as supported by the fact that this phenomenon occurs only at the lowest surface concentrations of the dye.

Low-temperature optical constants of amorphous silicate dust analogues

Context. Cosmic dust models are key ingredients in advancing our understanding of astronomical environments as diverse as interstellar clouds in galaxies, circumstellar envelopes around evolved and young stars, and protoplanetary disks. Such models consist of several dust populations, each with different compositions and size distributions. They may also consider different grain shapes, although most models assume spherical grains. All include a component of silicate dust. The absorption and emission properties of these dust components are calculated from the optical constants of each dust material which have various experimental, phenomenological, and theoretical origins depending on the model. Aims. We aim to provide the community with new sets of optical constants for amorphous silicate dust analogues at low temperatures. The analogues consist of four Mg-rich silicate samples of stoichiometry ranging from enstatite to olivine, and of eight samples of Mg- and Fe-rich silicates with a pyroxene stoichiometry and differing magnesium and iron content. Methods. We calculated the optical constants from transmission measurements using the Kramers-Kronig relations, assuming that the grains are small compared to the wavelength and prolate in shape with axis ratios of 1.5 and 2 for the Mg- and Fe-rich samples, respectively. Results. New optical constants for silicate dust analogues of various compositions were calculated over the wavelength range from 5 to 800 µm or 1000 µm, depending on the sample, and at temperatures of 10, 30, 100, 200, and 300 K. We determined the uncertainties on the derived optical constants based on the assumptions used to calculate them. To facilitate the use of these data in cosmic dust models, we provide optical constants extrapolated outside the measured spectral range into the ultraviolet(UV)/visual(VIS)/near-infrared(NIR) and millimetre and centimetre wavelength ranges, as well as formulae that can be used to interpolate the optical constants at any temperature in the range 10–300 K.

Degradation behavior of heat-treatment silicate adhesive under special working conditions

Inorganic adhesive is widely used in the sealing and connection of electronic devices. Its insulation is highly important in the performance of installation. In this paper, the insulation resistance and tensile strength of different composite silicate samples were measured by test machines. The morphology and surface composition were analyzed by electronic microscope and energy spectrum analyzer. The results show that: In a humid environment, the resistance insulation of adhesive increases with the rising of heat treatment temperature, and decreases with the increment of wet environment. When the modulus ratio of colloidal liquid is in the range of 7.2~9.1 and the heat-treatment temperature is larger than 600°C, the effect of moisture resistant is remarkable. The tensile strength of adhesive deteriorates with the increasing of humidity. Furthermore, with ascending heat treatment temperature, the tensile strength rises when the modulus ratio of adhesive is less than 7.2, and declines when it is more than 9.1.

Solidus melting of pyrolite and bridgmanite: Implication for the thermochemical state of the Earth's interior

Melting properties of the deep mantle remain controversial due to experimental difficulties; e.g., reports of solidus temperatures of mantle-relevant compositions span over ∼700 K at 2000 km depth. This situation limits our understanding of the thermochemical state of the Earth's interior. Using the laser heated diamond anvil cell (LH-DAC), we performed new experimental determination of the solidus profile of ultra-dry pyrolite and the solidus of two compositions of (Mg,Fe)(Si,Al)O3 bridgmanite (Bg). Melting was detected (i) from -the correlation between laser power and sample temperature, -changes of sample texture and -the level of visible light absorption, for all samples, (ii) using X-ray diffraction, for the MgSiO3 composition and (iii) after scanning electron microscope observations, for selected Fe-bearing samples. Special care was given to using ultra-dry experimental chambers and to determination of sample temperature. In particular, we discuss the wavelength-dependent thermal emission of silicate samples, which lowers the solidus by 100 to 300 K, compared to the grey-body assumption.The solidus of MgSiO3-Bg is in good agreement with previous reports using ab initio calculations and shock wave experiments. We observe a net decrease in the solid-liquid Clapeyron slope at 60(3) GPa and 4400(200) K, which can be related to rapid pressure-induced coordination change of Si in the melt. (Mg0.955,Fe0.045)(Si0.993,Al0.007)O3 Bg melts 600–800 K lower than MgSiO3-Bg. Its solidus evolves smoothly with pressure, suggesting progressive Si coordination change in the melt. In the pressure range investigated (24–135 GPa) Clapeyron slopes suggest rapid decrease of the volume of fusion, from 14 to 2% for MgSiO3 and from 9 to 3% for (Fe,Al)-bearing Bg, assuming congruent melting. By comparing the solidii of various silicates, it appears that the higher the number of cations, the less pronounced is the curvature of the solidus. This observation suggests that the relatively ordered structure of simple liquid compositions with a limited number of distinct network-modifying cations frustrates the coexistence of tetrahedrally and octahedrally coordinated Si polyhedral.The solidus of pyrolite presents a smooth evolution from 2200(100) K to 3950(200) K in the same pressure interval. This is very similar to our previous work on chondritic-type mantle. The new solidus is 200–300 K lower than that of KLB-1 peridotite, which can be related to more incompatible elements in pyrolite. It remains problematic that our solidus plots several 100 K higher than other recent measurements performed on pyrolite; we discuss the possibility of a higher water content in previous samples, compared to our experiments. Assuming a dry lowermost mantle, our results imply a core-mantle boundary temperature lower than 3950(200) K. Modeling the melting diagram at the core-mantle boundary suggests a pseudo-eutectic melt significantly depleted in SiO2, compared to the composition of the mean mantle.

Rapid Radiolytic Degradation of Amino Acids in the Martian Shallow Subsurface: Implications for the Search for Extinct Life.

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of ∼1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just ∼20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.

Experimental Study on the Mix Ratio of Restored Heritage Building Adobe

The reciprocating action of the external environment gradually reduces the mechanical properties and water stability of original heritage buildings, resulting in the gradual loss of their cultural value. In this paper, the adobe for the construction of raw soil and cultural relics in western Henan is taken as the research object. The local plain soil is used as the raw material, and the adobe samples are prepared with modified materials such as quicklime and sodium methyl silicate, in order to improve its mechanical properties and water stability. The degree of correlation between the compressive strength, capillary water absorption, pH value, particle size distribution, and the electrical conductivity of modified raw adobe, as well as the modification mechanism of the microstructure, was studied. The results show that the addition of quicklime and sodium methyl silicate can enhance the compressive strength and water resistance of the modified raw adobe, and the optimum dosage is 1.5% sodium methyl silicate; with the increase of the curing age, the compressive strength of the single-mixed quicklime sample, the single mixed sodium methyl silicate samples, and the composite sample were increased by 1.94 times, 12.6 times and 2.61 times, respectively, compared with the plain soil samples, and with the increase of compressive strength, the pH, conductivity and capillary water absorption of the samples decreased continuously. It is evident from the particle gradation test and SEM images that the internal pores of the samples in the modified group become smaller, and the particle structure of the sample doped with sodium methyl silicate is the densest. The results of the study provide support for the restoration of the soil and cultural-relic buildings.

Sorption of Strontium to Uraninite and Uranium(IV)-Silicate Nanoparticles.

Spent nuclear fuel contains both uranium (U) and high yield fission products, including strontium-90 (90Sr), a key radioactive contaminant at nuclear facilities. Both U and 90Sr will be present where spent nuclear fuel has been processed, including in storage ponds and tanks. However, the interactions between Sr and U phases under ambient conditions are not well understood. Over a pH range of 4–14, we investigate Sr sorption behavior in contact with two nuclear fuel cycle relevant U(IV) phases: nano-uraninite (UO2) and U(IV)–silicate nanoparticles. Nano-UO2 is a product of the anaerobic corrosion of metallic uranium fuel, and UO2 is also the predominant form of U in ceramic fuels. U(IV)–silicates form stable colloids under the neutral to alkaline pH conditions highly relevant to nuclear fuel storage ponds and geodisposal scenarios. In sorption experiments, Sr had the highest affinity for UO2, although significant Sr sorption also occurred to U(IV)–silicate phases at pH ≥ 6. Extended X-ray absorption fine structure (EXAFS) spectroscopy, transmission electron microscopy, and desorption data for the UO2 system suggested that Sr interacted with UO2 via a near surface, highly coordinated complex at pH ≥ 10. EXAFS measurements for the U(IV)–silicate samples showed outer-sphere Sr sorption dominated at acidic and near-neutral pH with intrinsic Sr-silicates forming at pH ≥ 12. These complex interactions of Sr with important U(IV) phases highlight a largely unrecognized control on 90Sr mobility in environments of relevance to spent nuclear fuel management and storage.

Reverse cationic flotation of iron ore by amide-amine: bench studies

This study evaluated the performance of a new collector amide-amine compared with a traditional etheramine in conventional reverse cationic flotation of a siliceous itabirite sample of the Quadrilátero Ferrífero (d80 = 116 μm, 40% Fe and 41.2% SiO2). Statistical design of experiments was used to determine the influence of pH, collector and starch dosages on mass and Fe recoveries, Fe and SiO2 grade in the concentrate, Fe grade in the tailings and Gaudin's selectivity index (S.I). For the amide-amine, starch had no significant effect on mass recovery and in the Fe and SiO2 grade in the concentrate. For the same dosages, it was found that amide-amine was less selective than etheramine. However, at higher dosages, at pH 8 and without starch, concentrates with Fe >65% and SiO2 <5% grades were obtained, similar to the grades obtained with etheramine and starch at pH 10.5. The mass and Fe recoveries were higher and consequently, the Fe grades in the tailings were lower. These results indicate that, despite the higher dosage required, amide-amine is selective without starch, which is very interesting from the economic point of view and simplification of the process route, implying a great potential for its industrial application.

VNIR reflectance spectra of silicate-graphite mixtures: The effect of graphite content and particle size

We report the VNIR (350–2500 nm) reflectance spectra of a suite of silicic samples mixed with graphite. We used three end-member materials with different chemical composition in order to have a comprehensive understanding of the effect of opaque minerals on reflectance spectra of silicic rocks. To decouple the effect of granulometry and graphite content on reflectance properties, we first measured the reflectance spectra for each end member at different grainsizes (between ⁓20 to 250 μm). Three selected grainsizes for each end-member were then mixed with graphite in the graphite/end-member weight ratio 1 to 5%. For each spectrum we evaluated the main band parameters (position, area, depth). Moreover, we also proposed and discussed the use of an additional parameter, the band centroid. Our results confirm that graphite mixed with silicate materials reduces albedo and decreases the spectral slopes and the spectral contrast of the mixtures. We discussed the subtle interplay between grain size, graphite content and chemical composition of the mixtures. We showed how graphite decreases the spectral slopes of the graphite-silicate mixtures proportionally to iron content (albedo) of the mixtures: low iron (bright) materials are more sensitive to spectral slope variation (decrease) as a function of graphite content. Finally we show how spectral slope influences the measured band parameters.

Characteristics and evolution of the Etili silica sinter epithermal deposits, Çanakkale – Turkey: Relation to alkali chloride vs acid-sulfate fluids

The Oligo-Miocene Etili epithermal deposits are a well-preserved fossil geothermal system in the Çanakkale Region and is one of the largest fossil siliceous hot spring deposits of Turkey. Main E-W and NE-SW trending faults systems occur with minor NW-SE fracture systems perpendicular to the main faults. Silica-rich deposits are commonly observed in or on the calc-alkaline tuffs, ashes and pyroclastic rocks that were the products of the magmatism controlled by the extensional tectonic regime.The Etili epithermal system was examined at two representative locations including the Hamamtepe and Muratlar sites. Morphologies of the proximal apron were defined by lithofacies that included silica infiltrate, spring conduits, nodular and finely laminated geyserite, sinter clast breccia, silicified volcanic rocks, and epithermal veins. Microfossils were detected in mat structures developed in the proximal apron. The silica deposits have low abundances of altered mineral assemblages (e.g., kaolinite, halloysite, and alunite), which are otherwise commonly observed in the region. The origin of the Etili Fossil Silica Sinter Region (EFSSR) was constrained by using geochemical and isotopic data. δ18O and δD isotopic values of kaolinites ranged +9.4/+9.6 ‰; to 84/−74 ‰ respectively. δ18O isotopic values from siliceous and silicified samples ranged from 8.3 to 18.4 ‰, which shows two different formation types for the Etili Fossil Silica Sinter Region. We hypothesized hypogene origins for the kaolins and a mixed hypo/supergene origin for siliceous and silicified samples. The calculated model formation temperature from the δ18O values of the silica and siliceous samples is in the range of 63° to 140 °C. δ34S isotopic values of alunite ranged from −19.6 to +16.6 ‰, which also indicated two different sources that include magmatic hydrothermal and meteoric waters affected by bacterial activity. The timing of acid-sulphate alteration can be grouped into three periods by 40Ar/39Ar dating of alunites. These ages are: (A) 32.4 ± 1.2 to 22.6 ± 0.22 Ma in the Muratlar silica site, (B) 12.3 ± 0.3 to 15.2 ± 0.3 Ma in the northern part of the Hamamtepe site and (C) 5 ± 0.18 to 7 ± 0.3 Ma in the southern part of the Hamamtepe silica site. These consistent findings show that the emplacement periods of the Evciler pluton and the ages of alteration deposits are similar to each other. Silica sinters and geyser mounds represent very late stage near-neutral pH alkali chloride geothermal activities. The epithermal deposits in the EFSSR comprises a complex history of three different hydrothermal processes, each of which have different compositional and temporal emplacement periods related to the Evciler pluton.

Quartz types in the Wufeng-Longmaxi Formations in southern China: Implications for porosity evolution and shale brittleness

Quartz is an important component of shale and has a significant influence on shale physical properties. However, the specific effects that different quartz types exert on shale porosity evolution and brittleness remain unclear. A series of experiments including petrographic observations, geochemical analyses, and triaxial compress experiments were conducted on shale samples from the Wufeng-Longmaxi Formations in southern China. The Wufeng-Longmaxi samples have been classified into siliceous shale, argillaceous shale, and mixed shale. Several quartz types were identified in the shale samples, including extrabasinal detrital quartz and authigenic quartz (microcrystalline quartz, quartz overgrowths, and bioclastic quartz). Based on the different origins, the authigenic quartz was divided into biogenic quartz derived from the dissolution of siliceous organisms and S–I quartz derived from the conversion of smectite to illite. Bioclastic quartz, most microcrystalline quartz, and most quartz overgrowths are biogenic quartz. A small number of quartz overgrowths and microcrystalline quartz are S–I quartz. The quartz content of different genesis processes was quantitatively calculated using major and trace elements data collected via XRF. Quartz types in siliceous shale samples are dominated by biogenic quartz (avg. 49%). Extrabasinal detrital quartz is the primary quartz type in argillaceous shale samples (avg. 68%) and mixed shale samples (avg. 50%). Porosity reduction mechanisms in most of the Wufeng-Longmaxi shale samples are primarily compaction-dominated. Biogenic quartz acts as a pore protector rather than destroyer, while S–I quartz derived from the conversion of smectite to illite acts as a pore destroyer rather than protector. The brittleness index (BI) of siliceous shale samples is the highest of all the shale samples since the abundant biogenic microcrystalline quartz particles dispersed within the shale matrix connect rigid grains to form an interconnected force framework.

A Laboratory-driven Multiscale Investigation of X-Ray Induced Mass Loss and Photochemical Evolution in Cosmic Carbon and Silicate Dust

Abstract We present the results of an integrated laboratory and modeling investigation into the impact of stellar X-rays on cosmic dust. Carbonaceous grains were prepared in a cooled (&lt;200 K) supersonic expansion from aromatic molecular precursors, and were later irradiated with 970 eV X-rays. Silicate (enstatite) grains were prepared via laser ablation, thermally annealed, and later irradiated with 500 eV X-rays. Infrared spectra of the 3.4 μm band of the carbon sample prepared with benzene revealed 84% ± 5% band area loss for an X-ray dose of 5.2 ×1023 eV.cm−2. Infrared spectra of the 8–12 μm Si–O band of the silicate sample revealed band area loss up to 63% ± 5% for doses of 2.3 × 1023 eV.cm−2. A hybrid Monte Carlo particle trajectory approach was used to model the impact of X-rays and ensuing photoelectrons, Auger and collisionally ionized electrons through the bulk. As a result of X-ray ionization and ensuing Coulomb explosions on surface molecules, the calculated mass loss is 60% for the carbonaceous sample and 46% for the silicate sample, within a factor of 2 of the IR band loss, supporting an X-ray induced mass-loss mechanism. We apply the laboratory X-ray destruction rates to estimate the lifetimes of dust grains in protoplanetary disks surrounding 1 M ⊙ and 0.1 M ⊙ G and M stars. In both cases, X-ray destruction timescales are short (a few million years) at the disk surface, but are found to be much longer than typical disk lifetimes (≳10 Myr) over the disk bulk.

Non-matrix-matched calibration of Mg isotopic ratios in silicate samples by fs-LA-MC-ICP-MS with low mass resolution under wet plasma conditions

Accurate and precise Mg isotopic analysis by fs-LA-MC-ICP-MS can be performed with low mass resolution and non-matrix-matched calibration.