Clay Minerals Research Articles

Determination of a normal orogenic palaeo-geothermal gradient with clay mineral and organic matter indices: a review

A collection of large data sets from different orogenic belts was compiled for a correlation between organic matter (OM) versus clay mineral (CM) indices calibrated with the vitrinite reflectance, (VR) vs Kübler-Indices (KI) method. Data selection was based on a normal geothermal gradient (25 to 35 °C/km) as determined in previous studies, e.g. by maturity modelling and clay mineral reaction progress calculations. In the Lower Austroalpine (Eastern Switzerland, European Alps) a 20 myr lasting metamorphic overprint caused an OM–CM thermal equilibrium among the indices used. The observed correlation enables to determine gradual changes in metamorphic factors such as pressure, temperature and time causing sensitive shifts of the gradient slope in the range of normal gradients. For New Caledonia, an identical correlation has been determined. Prior to re-equilibration of the VR/KI indices, sediments in New Caledonia of diagenetic to incipient metamorphic grade underwent a high-pressure subduction event. VR/KI indices are in or close to equilibrium, while slight differences in OM vs CM indices allow for a better understanding of polyphase conditions, especially with respect to pressure. Temperature estimations are identical despite of their poly-phase metamorphic history, which was mainly controlled by the last orogenic thermal event lasting > 5 to < 10 myr. In the eastern Helvetic Alps and Northern Calcareous Alps similar correlations were found with slightly different slopes. Comparison between different regions is possible when using KI standardization and same data discrimination. In both parts of the Alps a complex thermal history of short durations (< 5.0 myr for the Northern Calcareous Alps to 10 myr for the Helvetic Alps) caused similar VR/KI trends, but disequilibrium is suggested by weaker regression parameters. The following correlation is calculated for a moderate geotherm (55 to 74 mWm2, mean = 61 mWm2) and normal temperature gradient conditions (25 to 35 °Ckm−1): KI = 1.134e−0.305VR, (R2 = 0.880, n = 462) with VR given as %Rmax, KI as Δ°2θ (limited to values between 0.2 to 1.0 Δ°2θ). With increasing depth (z) a VR gradient of 1.4 ± 0.2%Rmaxkm−1 is determined and a KI gradient of 0.09 ± 0.002 Δ°2θ km−1 is observed. The study illustrates that a normal geotherm can be described by VR/KI correlation, even if different heating episodes may occur. For the detection of a poly-phase or plurifacial thermal history, several indices of clay minerals and organic matter with very different kinetics should be used, as e.g. demonstrated by strong differences in smectite content at equal VR/KI values versus structural depth. A specific interest is given to the correlation of vitrinite like solid bitumen reflectance as an alternative method to VR, the persistent preservation of liptinite macerals and the stability range of clay minerals and sub-greenschist facies critical minerals compared with VR/KI data. Until now, despite the Alps in this study, systematic liptinite maceral studies have not been published in other orogenic settings.

Unusual cobalt behaviors and enrichment in cobalt-rich crust from the Magellan seamounts in the Western Pacific

Marine cobalt-rich (Co-rich) crusts are submarine critical metal resources with high economic value. In this study, detailed in-situ fine-scale morphological, mineralogical, and geochemical analyses were conducted on Co-rich crust from the Western Pacific. The Co-rich crust can be divided into three layers: (1) Layer 1 is the oldest anthracite layer and contacts with the substrate, showing a very dense laminated/columnar texture. Layer 1 can be further divided into two distinct sublayers: a lower black, massive, dense sublayer (Layer 1–1) and an upper black-to-brown sublayer (Layer 1–2). (2) Layer 2 is porous and locally vuggy, and its pore space is filled with a large amount of silicate detrital minerals and clay minerals. (3) Layer 3, on the top, is black and dense, with a dendritic, columnar/laminated texture. Co is very unevenly distributed throughout the whole crust, with three distinct Co-rich areas. Layer 3 is a typical hydrogenetic crust and has not undergone late alteration. The main processes for Co enrichment are specific adsorption-oxidation on Mn-oxides and the structural incorporation of Co3+ into Mn-oxide phases. The average Co content of the Layer 3 is much higher than that of the other two layers. The presence of abundant detrital and clay minerals, along with high levels of Al, Si, and Ti in Layer 2, indicates the incorporation of terrigenous material, resulting in a high average growth rate. However, these processes are not conducive to Co enrichment. In the phosphatized Layer 1, fluctuations in element content are significantly greater than in the upper, non-phosphatized layers. Phosphatization has resulted in the partial decomposition of the initial Co-rich micro-layers, which may have reactivated and migrated Co, contributing to secondary Co enrichment.

Mudstone diagenesis with depth and thermal maturity in the Cenomanian–Turonian Eagle Ford group. PART II: Diagenetic processes and paragenetic sequence

The Cenomanian–Turonian (C–T) Eagle Ford Group (EFG) is composed of massive, laminated, and/or burrowed limestones, marls, and lime mudstones deposited on the drowned south Texas shelf below storm-wave base. A burial diagenesis investigation using seven cored wells from shallow to deep burial (depth ranges from 7684 to 13,670 ft [2342 to 4166.6 m]; BHT from 183 to 285 °F [83.9–140.6 °C]) and from east (San Marcos Arch) to west (Maverick Basin) delineated a complex diagenetic history as a result of changes in water chemistry, redox condition, and burial history. The second part of this comprehensive study shows the variety of diagenesis and paragenesis. This study focuses especially in the organic-rich Lower Eagle Ford (LEF) member deposited largely under anoxic/euxinic conditions. Processes such as near seafloor sulfate-reduction, Fe-reduction, and methanogenesis drive various chemical reactions during lithification. Feldspar diagenesis included albitization and transformation of K-feldspar to kaolinite and albite, and from kaolinite to Mg-chlorite with depth. Clay mineral diagenesis is complex with authigenic kaolinite, mixed kaolinite/Mg-chlorite, and Mg-chlorite form in biota tests and matrix. Additionally, calcite dissolution, burial dolomitization, late Fe-chlorite replacement, and oxidation of pyrite to marcasite are also observed. Detritus-derived smectite starts to transform to mixed layered clay, illite-smectite (I/S) in the oil window; however, illitization trends were not observed in depth. This is because most smectite forms from alteration of volcanic ashes and the volcanic origin of the disorientated smectite did not follow regular illitization kinetics. The increase in Mg content from illitization transforms not only the kaolinite to chlorite, but precipitates authigenic dolomites. The clay minerals precipitated in the original interparticle pores, further reducing porosity, and impacted permeability, fluid saturation, wettability, and capillary pressure. With thermal maturation, bitumen and oil conversion increases oil-wetness of the rock and the resistivity measurement from wireline logs.

Morphology and chemical composition of mineral particles in a special dust storm with high relative humidity in North China

A special dust storm characterized by high PM10 mass concentrations (921.9 ± 632.3 μg m−3) and high relative humidity (RH; 60.1 % ± 11.1 %) was observed on March 22–24, 2023 at a coastal city of North China. Aerosol particles of PM10 were analyzed by a scanning electron microscope coupled with energy dispersive X-ray and an ion chromatograph. The results showed that individual mineral particles were dominated by clay minerals, followed by quartz, feldspar, and carbonate. Bulk water-soluble inorganic ions analysis showed that SO42- mass concentrations varied from 3.7 μg m−3 to 23.3 μg m−3 with an average value of 12.4 μg m−3. However, their mass ratios to PM10 were relatively stable, being 1.15–2.01 % with an average value of 1.49 % ± 0.25 %, similar to the value near the dust sources (Tengger Desert). Although S-containing individual mineral dust varied from 5.2 % to 70.7 %, the average weight ratio of S on individual mineral dust was 2.1 %, much lower than that of non-dust periods (11.0 %). The results suggested limited sulfate formation on mineral dust surfaces even under high RH. In contrast, NO3-, which was very limited in dust sources, varied from 0.21 % to 4.11 % of the total PM10 with an average value of 1.61 % ± 1.07 %. The research highlighted that nitrate formation has exceeded sulfate formation during severe dust storm episodes, which might because the atmospheric compositions in China have changed significantly with a high mass ratio of NO2/SO2 after the implementation of the strict emission control measures.

An evaluation of the consistency of data and models for performance assessment: Divalent metal sorption on montmorillonite

A detailed analysis of literature data on the retention of divalent metal by purified montmorillonite or montmorillonite-rich material (e.g. bentonite) was conducted. Data for which sufficient experimental conditions were available were modeled with the 2SPNE SC/CE model available in the literature, and with a “minimalist” model, which uses a minimum number of parameters to reproduce the data.A successful data modeling could only be achieved if considering (i) cation exchange competition with aqueous Ca2+ and Mg2+, originating from the dissolution of the clay mineral itself or accessory minerals and (ii) precipitation, at high pH, of phases incorporating the divalent metal of interest. However, in many studies, the concentration of aqueous Ca2+ and Mg2+ and, more generally, a full characterization of solution composition (e.g., Si, Al, dissolved organic carbon, alkalinity) is not provided, thus impeding accurate data modeling. Further difficulties stem from uncertainties related to the nature of the solids precipitating at high pH and missing or inaccurate thermodynamic data related to mineral solubility.Log KD values cannot be predicted from available literature data with an accuracy better than ±1 log unit, without sorption data obtained on a material representative of in situ conditions. In addition, the most reactive sites, commonly referred to as strong sites, which have been characterized only on some, but not all, reference clay materials, should not be considered in blind predictions based on the mineralogical composition of clay materials.

Role of modified calcium montmorillonite and 5 A zeolite in microstructure and efflorescence formation of metakaolin-based geopolymer

To reduce the efflorescence extent of metakaolin (MK)-based geopolymer, this study introduced thermally activated modified calcium montmorillonite (MT) and 5 A zeolite (ZT) into MK-based geopolymer, and the optimal mixing ratio was acquired by response surface methodology. The effect of the two modified clay minerals on the microstructural and mechanical properties of the MT-ZT-MK geopolymer was explored by compressive strength testing, phase analysis (XRD and FTIR), pore structure analysis (MIP), and morphology analysis (SEM-EDS). To investigate the performance and mechanism of efflorescence inhibition of the ternary geopolymer, the cation concentration in the leaching solution was detected by inductively coupled plasma atomic emission spectrometry (ICP-OES), and the efflorescence area of the geopolymer was calculated using Image Pro Plus (IPP) software. The results of the experiment showed that the optimal mixing ratio, as determined by RSM, was 1.5 wt% of modified MT and 2.9 wt% of modified ZT, with the highest compressive strength at 65.1 MPa and the lowest degree of efflorescence after 28 days of curing. It can be concluded that the two clays gradually exhibit the effect of cation exchange and internal curing. The pore structure is optimized and (N, C)-A-S-H gels are formed with the extension of curing time. On the other hand, the lesser extent of efflorescence possibly is attributed to the restricted channels for Na+ in the matrix to undergo carbonation with CO2 in the air.

Geochemical influences of hydrogen storage in depleted gas reservoirs with N2 cushion gas

Geochemical investigation of hydrogen (H2), brine, rock formations, and residual gases (nitrogen – N2, methane – CH4, and carbon dioxide – CO2) is crucial for understanding H2 storage processes in depleted gas reservoirs. This study examines the effects of injecting a gas mixture (60% H2 + 30% N2 + 5% CH4 + 5% CO2) into Bandera Grey sandstone with notable clay mineral content. The experiment lasted 50 days at 42 °C, 1350 psi, and 5 wt% NaCl brine, with detailed analytical characterization before and after aging. Results show minimal sample reactivity, causing slight alterations in petrophysical characteristics. Dissolution primarily affected dolomite and barite minerals, while illite and kaolinite caused pore blockage. Gas chromatography data indicate only 0.45% of injected H2 is lost (via dissolution in brine and reaction with CO2), CH4 increased by 6.22%, N2 remained stable, and CO2 decreased by 1%. These results provide valuable insights into the feasibility and safety of utilizing depleted gas reservoirs for H2 storage.

MINERAL PHYSICS ANALYSIS OF ALLUVIAL ROCKS AS A SOURCE OF SHALLOW HYDROCARBON SEEPAGE IN BELIS VILLAGE, WARU BASIN, EASTERN SERAM ISLAND, MALUKU PROVINCE

Belis Village is located in the Waru basin adjacent to the Bula basin on the eastern part of Seram Island and has potential shallow hydrocarbon manifestations. This research aims to determine the mineralogical characteristics of the rocks that make up shallow hydrocarbon manifestations at the research location. The research method used is physical analysis of minerals including petrographic analysis and XRD methods. The analysis results of the XRD method show an abundance of quartz minerals at 58%, followed by clay minerals at 35%, opaque minerals at 25%, and the rest in the form of cavities while feldspar minerals are secondary minerals. The results of the XRD analysis show that the more dominant mineral is protoenstatite (MgSio3) with an average abundance of 70.33% as a carrier of shallow hydrocarbon seeps, Quartz (SiO2) with an average abundance of 18.46%, and Clinoestatite with an average abundance of 11.21% as a mineral associated with shallow hydrocarbon seeps.

Effect of secondary processes on the petrophysical properties of sand rock of the tanopchin formation of the Tambey field (Yamalo-Nenets autonomous okrug)

Relevance. Finding the correlation between filtration-capacitive properties and secondary processes helps to identify missed oil and gas deposits. Traditional methods of processing geophysical information are becoming less and less effective, and accordingly there is a need to introduce new techniques for detecting missed hydrocarbon deposits. Aim. To study the effect of secondary processes on the filtration and reservoir properties of rocks in the productive lower strata of the tanopchin formation of the North Tambey license area, located within the Tambey field, using materials from geophysical surveys of wells and core data. Methods. The statistical-correlation interpretation method represents a significant breakthrough in the field of interpretation of well logging data. It allows for a more accurate interpretation of data from existing reservoir studies, which makes it possible to identify productive sections of wells where hydrocarbons could not be detected by traditional methods. Statistical correlation interpretation is carried out on the basis of data from secondary geochemical processes occurring in the formation. The scientific novelty. Identification of the relationship between the intensity of secondary processes and the petrophysical properties of the rocks of the Lower Cretaceous productive horizon of the Tambey field (Yamalo-Nenets autonomous okrug). Results and conclusions. The author has determined the dependence of the filtration-capacitive properties of rocks on the intensity of secondary geochemical processes. It was established that secondary geochemical processes such as carbonatization and pyritization worsen reservoir properties, while kaolinization and pelitization lead to an improvement in the filtration and reservoir properties of reservoir rocks. The paper explains the mechanism of effect of secondary processes on filtration-capacitive properties. Pelitization of potassium feldspars leads to the formation of three-layer clay minerals, which have the largest sorption surface area and cation exchange capacity; as a result, the reservoir capacity increases, which leads to an increase in permeability several times.

Mineral composition of lake Sabakty sediments as an indicator of paleoclimate, Southern Urals, Russia

Relevance. Reconstruction of climatic changes based on the lacustrine sediments of lakes makes it possible to identify climatic trends and events in the late Quaternary. The Urals is considered as one of the climatic divisions, therefore, studies of the conditions of lake sedimentation, including climatic ones, are relevant in this area. Aim. To study mineral composition as an indicator of paleoclimate of Lake Sabakty sediments. Object. Core of Lake Sabakty sediments (length is 298 cm). The age of the core is ~25 thousand years old. Materials and methods. Sampling was carried out taking into account seismoacoustic data, lithological description, as well as measurements of magnetic susceptibility and radiometric dating data. The granulometric analysis was carried out by laser granulometry using a Bluewave particle size analyzer (Microtrac, USA) combined with a sample loading and circulation system with an integrated ultrasonic dispersant. Mineral composition of the sediments was determined using the D2 PHASER X-ray diffractometer and the Merlin auto-emission scanning electron microscope. Results. The predominance of the siltstone fraction was established. The mineral composition is characterized by the predominance of allotigenic minerals in sediments (quartz, microcline, albite, mica, chlorite, mixed-layer clay minerals, hornblende, kaolinite) according to X-ray diffraction and electron microscopy. Autigenic minerals include biogenic silica (cristobalite, tridymite), pyrite, carbonates (calcite, dolomite), sulfates (gypsum, barite). Conclusions. The ratio of allogenic and autogenic components reflects the changes in the accommodation of the reservoir and the supply of clastic material associated with changes in climate humidity. Changes in climate humidity are reflected in changes in the contents of carbonate and sulfate minerals. At the beginning of sedimentation, Lake Sabakty was shallow and mineralized due to climate aridization, which probably included the global Bond 8 event (~26000–11700 BP). The study of the mineral composition of the sediments of Lake Sabakty allowed us to establish the events of climate aridization: ~10000 BP, ~7600 BP, ~6900 BP ~1900 BP and ~1400 BP. In Sabakty Lake, there is a bright episode of a decrease in climate humidity in the range of ~7300-5200 BP, which is marked by an increase in carbonate content up to 70% and the detection of gypsum at ~6900 BP.

Layered Silicates Exhibiting MOF-Like Gate-Opening Behaviors in Liquid-Phase Adsorptions: Experimental and Theoretical Investigations.

Layered silicates, including clay minerals, can be used as liquid-phase adsorbents in many important applications. However, because their two-dimensional interlayer space is narrow and not entirely opened due to the presence of interlayer species, guest species are forced to penetrate while expanding the interlayer space, which limits their adsorption performances compared with microporous materials such as MOFs and zeolites. Herein, as reported for the adsorption of gaseous species on flexible MOFs, we report a layered silicate that exhibits gate-opening adsorption in liquid phases. This layered silicate, synthesized via dilute acid treatment of the parent sodium-type, exhibits an abrupt increase in the basal spacing (layer thickness + interlayer space) to reach a plateau even at an earlier stage of benzoic acid adsorption from acetonitrile, whereas a typical layered silicate, magadiite, exhibits a gradual increase in the basal spacing as adsorption progress under identical conditions. The layered silicate shows an excellent adsorption capacity and rate for benzoic acid uptake from acetonitrile, which is considerably higher than that of magadiite. With comprehensive adsorption tests using different adsorbates and solvents, we propose that the layered silicate has zeolite-like but distorted, flexible open microchannels within each layer, and the intralayer microchannels can effectively and rapidly accommodate the solvent (acetonitrile) molecules, which are capable of expanding the framework to initiate the adsorption of aromatic compounds. The density function theory calculation revealed the adsorption mechanism, where the layered silicate accommodates acetonitrile in the intralayer microchannel followed by the interlayer space, and the former selectively plays a role as the adsorption site of aromatic compounds via exchange with acetonitrile.

Enhanced enrichment of rare earth elements during pedogenesis under subtropical climate

Rare earth elements (REE) are crucial strategic resources, and weathering-crust rare earth deposits are one of the primary sources. To systematically understand the geochemical behavior (e.g., enrichment and leaching) of REE in soils (or weathering crusts) formed from diverse parent rocks under varying climatic conditions, 171 soil profiles (weathering crusts) developed from three main types of parent rocks (granite, basalt, and carbonate rock) worldwide were studied. Granite shows the highest concentration of rare earth elements at 264 (interquartile range (IQR): 278) ppm, 171 (IQR: 151) ppm and 11.9 (IQR: 36.4) ppm in basalt and carbonate rock, respectively (median test: p &lt; 0.05). The median REE values within the soil profiles were significantly different (median test: p &lt; 0.05), with the concentration of 318 (IQR: 441) ppm, 267 (IQR: 217) ppm and 207 (IQR: 417) ppm in soils derived from granite, carbonate rock, and basalt, respectively. Principal component analysis (PCA) and Linear mixed-effects models (LME) revealed that soils developed from granite and basalt inherit the mineral characteristics of their parent rocks, with REE concentrations primarily influenced by the REE content of the parent rock and climate. In contrast, the REE concentrations in soils developed from carbonate rocks are predominantly controlled by climate. LME and correlation analysis indicates that the enrichment of REE (Q REE ) shows a trend of initially increasing and then decreasing with rising temperature and precipitation, due to variations host clay minerals. The greatest enrichment occurs in the subtropical region (mean annual temperature (MAT) = 15 ̶ 23 °C; mean annual precipitation (MAP) = 1000 ̶ 2000 mm); weathering-crust type REE deposits are primarily found in the subtropics.

Impurity Ions Mn&lt;sup&gt;2+&lt;/sup&gt; and Fe&lt;sup&gt;3+&lt;/sup&gt; as Paired Spin Labels for the Study of Structural Transformations in Phyllosilicates by the ESR Method

Impurity paramagnetic ions Mn2+ and high spin Fe3+ (S = 5/2) are shown to be very informative “paired spin labels” to investigate structural transformations in natural aluminosilicate clay minerals by ESR spectroscopy. Second derivative ESR (SD ESR) enables to detect minor narrow lines of the ions against the background of intense broad lines of other paramagnetic impurities. Complex SD ESR spectra of the ions are explained by the Jahn-Teller effect and hyperfine interactions with OH-groups. SD ESR spectra before and after heating (620°C and 900°C) proved transformations of octahedral crystal cells accompanied by the loss of the OH-groups, displacement of the ions to equivalent positions.

Distinct mechanisms controlling and influencing the supply of clay-sized sediments to the northern shelf of the Sea of Okhotsk since the Last Glacial Maximum

The Sea of Okhotsk is a transitional zone between East Asia and northwestern Pacific Ocean. As a result, its massive thick sediments contain numerous important records of geological past, such as the mechanisms of materials and energy exchanges. However, the scarcity of studies tracing the provenance of clay-sized sediments in the sea has limited the progress of reconstructing the paleoclimate of East Asia. In this study, clay mineral analysis was conducted on 31 surface stations and the LV87–54-1 core. These results were combined with grain-size to provide reliable evidence for distinct mechanisms controlling the influx of clay-sized sediments into the northern shelf of the Sea of Okhotsk since 23 ka. Results of provenance analyses suggested that clay-sized sediments in the northern shelf mainly originated from its northwestern shelf, the Okhotsk–Chukotka volcanic belt, and the Kamchatka Peninsula. Clay-sized sediments of the northern shelf was primarily transported from the northwestern shelf and the Okhotsk–Chukotka volcanic belt after 23 ka, while those analogues from the Kamchatka Peninsula increased after 11.7 ka. Based on variations in clay mineral ratios, sediments from the northwestern shelf were mainly transported by the North Okhotsk Countercurrent, wherein rapid millennial-scale variations were influenced by the high-latitude Arctic Oscillation (from the Last Glacial Maximum to the Last Deglaciation) and the low-latitude East Asian summer monsoon (including the Holocene), respectively. By contrast, the influx of clay-sized sediments from the western Kamchatka Peninsula might be mainly controlled by the intensity of the West Kamchatka Current. From the Last Glacial Maximum to the Last Deglaciation, north and northwest geostrophic winds dominated in winter, and the West Kamchatka Current shifted eastward. Since the Holocene, weakened north and northwest geostrophic winds, but strengthened east winds caused a series of rapid millennial-scale variations in the West Kamchatka Current.

Reactive transport of Cd2+ in porous media in the presence of xanthate: Experimental and modeling study

In mining regions, flotation reagents can interact with heavy metals, thereby increasing the complexity of their migration. However, most current studies solely focus on the migration of heavy metals, neglecting the influence of flotation reagents in their models concerning mining area pollution. This study developed the reactive transport model, Multisurface Speciation Model (MSM), which integrated the reaction processes of the three main soil components (iron oxides, organic matter, clay minerals) and ethyl xanthate (EX), a typical flotation reagent, with cadmium (Cd²⁺) to investigate the effects of EX on the transport and retention of Cd²⁺ in natural porous media under varying pH conditions. The study revealed that EX formed new adsorption sites for Cd²⁺, enhancing its retention and inhibiting transport with increased EX loading (0 to 2.5 mmol·L−1), while higher pH levels (ranging from 4 to 8) further strengthened the retention capability of Cd²⁺. The MSM further predicted the solid-phase concentration distribution of Cd²⁺ among various components. With increasing EX-loaded concentrations, xanthate became the dominant adsorbing component, accounting for 48.93 % to 95.31 % of adsorption, and competitively interacted with other components. Xanthate retention was lower under acidic conditions compared to neutral and alkaline environments. Sensitivity analysis highlighted the concentrations of iron oxide adsorption sites (SurfaOH, SurfbOH) as critical parameters in the models, underscoring the need for precise determination of soil physicochemical indicators. This study stressed the crucial role of flotation reagents and pH conditions in controlling heavy metal mobility, offering important insights for environmental management in mining regions.

Three-dimensional interpretation of magnetotelluric data at Fogo Volcano, Azores Islands

The resistivity structure of Fogo volcano and the seismically active Congro region of São Miguel Island has been determined by 3-D inversion from 44 magnetotelluric soundings to yield new insights into the internal architecture of this volcanic island. Following comprehensive testing of processing codes to yield optimum magnetotelluric responses from the collected time-series, a robust electrical resistivity model was obtained. Sensitivity analysis of various features from the inversion process was used to determine their reliability, and aid geological interpretation. The magnetotelluric data imaged, and provided new structural insights into the Ribeira Grande geothermal system on the northern flank of Fogo volcano, where a shallow low resistivity (1 - 5Ωm) region has strong correlation with borehole data, and is shown to be an excellent proxy for mapping temperature and clay alteration mineralogy. Beneath the central edifice of Fogo volcano and also throughout the Congro region, the geology is very resistive, however the new magnetotelluric observations do not yield any further constraints on the origin of the seismicity that poses threats to the local populations residing on this hazardous island.

Heavy metal migration and lithium isotope fractionation under extreme weathering of basalt on tropical Hainan Island, China

Basalt weathering can cause heavy metal enrichment in soils, and lithium isotopes serve as an effective tracer for this weathering process. However, the relations among weathering intensity, heavy metal migration, and Li isotope fractionation remain unclear. We conducted systematic examinations of a basalt weathering profile on tropical Hainan Island in China. The characteristics of mineralogy, elemental and Li isotopic geochemistry indicate that the profile has undergone changes from initial to advanced and ultimately extreme weathering stages. The corresponding dominant minerals are primary minerals, clay minerals such as kaolin-group, and the Al–Fe–Ti (hydro)oxides. The variations of Fe-group heavy metals within the profile are very similarly to that of Fe, exhibiting a pattern of loss-gain-loss. Newly formed secondary minerals preferentially incorporate lighter 6Li, leading to a gradual increase in Li content and a decrease in δ7Li. Due to the high δ7Li value of rainwater input, the ongoing impact of secondary mineral adsorption is partially counteracted. This results in the δ7Li of laterite and topsoil being maintained within a narrow range (−3.2‰ ∼ −1.9‰), despite the broader variation observed across the entire profile (−3.2‰ ∼ +2.8‰). Comparing basalt weathering profiles in different climatic zones reveals a very complex Li isotope behavior and its controlling factors. Therefore, it is essential to carefully evaluate the influence of atmospheric input, secondary mineral adsorption, dissolution, and redeposition processes on Li isotopes. Throughout the entire profile, Cr, Ni, and Cu exhibit enrichment relative to soil background values, indicating that the weathering of tropical basalt may pose potential environmental risks for these elements.

Tailor-made polymer tracers reveal the role of clay minerals on colloidal transport in carbonate media

HypothesisHost rock weathering and incipient pedogenesis result in the exposition of minerals, e.g., clay minerals in sedimentary limestones. Once exposed, these minerals provide the surfaces for fluid–solid interactions that control the fate of dissolved or suspended compounds such as organic matter and colloids. However, the functional and compositional diversity of organic matter and colloids limits the assessment of reactivity and availability of clay mineral interfaces. Such assessment demands a mobile compound with strong affinity to clay surfaces that is alien to the subsurface. ExperimentWe approached this challenge by using poly(ethylene glycol) (PEG) as interfacial tracer in limestone weathering experiments. FindingsPEG adsorption and transport was dependent on the availability of clay mineral surfaces and carbonate dissolution dynamics. In addition, PEG adsorption featured adsorption–desorption hysteresis which retained PEG mass on clay mineral surfaces. This resulted in different PEG transport for experiments conducted consecutively in the same porous medium. As such, PEG transport was reconstructed with a continuum-scale model parametrized by a Langmuir-type isotherm including hysteresis. Thus, we quantified the influence of exposed clay mineral surfaces on the transport of organic colloids in carbonate media. This renders PEG a suitable model colloid tracer for the assessment of clay surface exposition in porous media.

Sediment-Hosted Rare-Earth Elements Mineralization from the Dian-Qian District, Southwest China: Mineralogy and Mode of Occurrence

The Xuanwei Formation’s claystones in the Dian-Qian District of Southwest China are rich in rare-earth elements (REEs), suggesting their potential as a source of medium and heavy rare earths. However, the REE content in these rocks is lower than other types of rare-earth deposits, and the interrelationship among clay minerals is intricate. There is no direct evidence indicating the mineralization of REEs, limiting their beneficiation and extraction. The objective of this study is the characterization of REE distribution in the Dian-Qian District. The sedimentary rocks in this district are mainly composed of kaolinite, boehmite, quartz, rutile, and pyrite. The results of continuous chemical extraction of REE-rich claystone and transmission electron microscope (TEM) observations have confirmed that REEs occurred as florencite in the rocks, and that the ion-absorption state makes only a negligible contribution to the REE content. A close relationship between florencite and kaolinite makes traditional mineral processing operations very difficult. Combined with the properties of kaolinite, roasting-acid leaching was the efficacious approach for rare-earth resources extracted from the rare earth-rich clay rocks of the Xuanwei Formation.

Adsorption of dibenzothiophene sulfone using Fe3+ and Fe6+-impregnated clay adsorbents

In this study, the adsorption of dibenzothiophene sulfone (DBTO) was investigated using clay minerals as adsorbents. Raw bentonite (BR) and raw activated clay (ACR) were impregnated with Fe3+ and Fe6+, creating bentonite-Fe3+ (BF3), bentonite-Fe6+ (BF6), activated clay-Fe3+ (ACF3), and activated clay-Fe6+ (ACF6). The surface functional groups, surface morphology, and surface area of the raw and modified adsorbents were studied through Fourier transform infrared spectroscopy, a scanning electron microscope, and Brunauer, Emmett, and Teller analysis, respectively. Batch experiments on simulated oil were done to test the effect of adsorption time (0.5–24 h), adsorption dosage (0.3–1.5 g), and adsorption temperature (30–50 °C). The results of the experiments showed the suitability of the pseudo-second order kinetic model on the clay adsorbent and sulfone system. This suggests that chemisorption is the rate-limiting step of the reaction. Equilibrium isotherms indicated the adherence of DBTO onto BR and BF3 to the Freundlich model, implying the heterogeneous adsorption of the sulfones onto the adsorbents. The systems of DBTO with BF6, ACR, ACF3, and ACF6 showed a better fit with the Dubinin-Radushkevich model. This denotes that adsorption happens through the filling of sulfones of the micropores on the adsorbent. Lastly, thermodynamic studies revealed the endothermic and non-spontaneous nature of the clay adsorbents and sulfone systems. The experiments showed that the impregnation of Fe3+ and Fe6+ lowered the desulfurization ability of the adsorbents. This could be due to the iron ions being hard acids and the sulfones being soft bases, thus showing lower compatibility than the raw counterparts of the adsorbents. Comparison with related studies showed that the prepared adsorbents, namely BF3 (5.1 mg g−1) and BF6 (6.4 mg g−1), had a higher adsorption capacity than Ni2+-loaded activated carbon (4.9 mg g−1) and activated clay (4.1 mg g−1). The study shows that BR (7.2 mg g−1) is the best-performing adsorbent, which can be set as the direction for future research. This study is a step toward the commercialization of oxidative desulfurization methods.