Clay Assemblages Research Articles

Late Carboniferous marine-continental transitional sediments in the Datong Basin, North China: Mineralogical and geochemical characteristics and paleoenvironmental significance

To understand the sedimentary paleoenvironmental changes in the marine-terrestrial strata of the Upper Carboniferous Taiyuan Formation in the Datong Basin of North China, we generated mineralogical and geochemical data of the Tashan and Emaokou mines in the eastern Datong Basin. The study strata vertically comprise kaolinitic claystones in the upper and lower parts and calcareous mudstones in the middle. The kaolinitic claystones are primarily composed of kaolinite and quartz, with a small amount of illite, feldspar and siderite, whereas the calcareous mudstones comprise mixed-layer illite/smectite (I/S) clay and carbonate minerals, with a minor amount of quartz, kaolinite, feldspar, and siderite. The paleosalinity indicators (B/Ga, Sr/Ba, and paleontological detritus) indicate that kaolinitic claystones are formed in freshwater, whereas calcareous mudstones are formed in marine water. The redox-sensitive trace element ratios (U/Th and Ni/Co) and trace metal enrichment factors (MoEF and UEF) indicate that kaolinitic claystone and calcareous mudstone formed under oxic and anoxic–suboxic conditions, respectively. Clay assemblages, chemical alteration index (CIA), and the Sr/Cu ratios show that kaolinitic claystones and calcareous mudstones were deposited under hot, humid, intense weathering conditions and warm, humid, and moderately weathering conditions, respectively. Based on these data and combined with previous studies, we conclude that transgressive events caused the changes in sediments in the study area, and the occurrence of transgressive events is related to the global glacio-eustatic fluctuation and paleoclimate changes during the Late Paleozoic Ice Age (LPIA). Our results are essential for unraveling the relationship between the study area and global paleoenvironmental changes during the LPIA.

Sepiolite as a multifactorial indicator of paleoenvironments in the Chobe Enclave (northern Botswana)

The origin and evolution of clay minerals in sedimentary basins are usually influenced by changes in depositional hydrochemistry. The formation and preservation of rare fibrous magnesium-rich clay minerals, like sepiolite, are of interest in the Chobe Enclave, northern Botswana, as it occurred in a siliceous-rich intra-cratonic basin. New X-ray diffraction (XRD) data, scanning electron (SEM) and transmission electron (TEM) microscopy analyses, as well as geochemical data, are used to study the origin of authigenic sepiolite and the sub-environments related to its formation in the Chobe Enclave. The paleoenvironment record during the Late Pleistocene to Holocene demonstrates that the deposition in the region was preceded by an aluvial fan/fluvial deposits in humid conditions. The upper-basin catchment yielded a clay assemblage, including kaolinite and minor smectite amounts, now preserved in the Chobe as a detrital phase. The alluvial fan deposits were later overlain by deposits from lacustrine/palustrine environments where significant hydrochemical changes took place: during these changes, a fibrous clay mineral (authigenic sepiolite) formed in shallow lake/marshes in a closed system with low energy, under the influence of magnesium-rich and alkaline waters. The mineralogical and geometrical (diagenetic) relationships between the palustrine deposits (carbonate facies) and sepiolite point to a sequence of precipitation from an evaporitic system in which calcite, sepiolite, and finally amorphous silica follow one another. In addition, although the sepiolite parent solution was enriched from a water source concentrated in Mg2+, the presence of Ba2+ ions also emphasizes some spells of hydrothermal activity.

Compositional-structural characterization of the Opalinus Clay and Passwang Formation: New insights from Rietveld refinement (Mont Terri URL, Switzerland)

Middle Jurassic Opalinus Clay (OPA) in Switzerland and Southern Germany is considered as host rock for the disposal of heat-generating radioactive waste. For the present study, core samples from the Mont Terri rock laboratory (Switzerland) were investigated using a facies-based approach including mineralogical and geochemical analyses. Special focus was on the analysis of the degree of ordering of irregular illite-smectite interstratified clay minerals (I-S) responsible for sorption of radionuclides and swelling properties of the rocks.The investigations support the classification of OPA into five main facies (instead of the established threefold division) and into further subfacies. The facies concept was extended to the Passwang Formation (PWF). The amount of clay fraction varies in samples from the different facies, which is consistent with variations in cation exchange capacity (CEC). X-ray diffraction (XRD) analyses of the <2 μm fraction revealed a homogenous composition of the main constituents, namely R1-ordered I-S, kaolinite, and illite. Crystal structure based Rietveld refinement indicates strong similarities in the nature of disorder of the interstratified illite-smectite minerals for all investigated facies. The I-S-phase can be described with the R1 model, which is together with the amount of illitic layers in the I-S an indicator for a maximum burial temperature between 90 and 105°C. The amount of illitic layer in the I-S varies from 73%–85% for all refinements and ordering types, and in all OPA and PW facies and subfacies. This, together with the homogenous composition of the clay size fraction points to (1) a homogenous overprint of the clay assemblage during burial and/or (2) a uniform siliciclastic sedimentary supply throughout the sedimentation period of the OPA. The results of this study highlight the need to combine lithofacial studies with mineralogical investigations in order to adequately capture the variability of clay-rich host rocks under consideration for radioactive waste disposal.

Diagenesis of continental carbonates linked to the evolution of the flexural margin of the Triassic Sorocayense-Hilario rift sub-basin, Argentina

The lithostratigraphic units that conform the Sorocayense Group and fill the Sorocayense-Hilario sub-basin represent an alluvial-fluvial-lacustrine succession with significant volcanic supply during its deposition. They are namely the Cerro Colorado del Cementerio, Agua de los Pajaritos, Monina, Hilario and El Alcázar formations and present several carbonate levels. The genesis, diagenesis, and main controlling factors on continental carbonates present a means to understand basin evolution through the study of their petrography and chemical elemental composition through cathodoluminescence techniques. We have identified six microfacies: a) homogeneous micrite, b) bioclastic micrite, c) dolomicrite, d) laminated micrite, e) oncolitic packstone, and f) sparitic carbonate. Among these microfacies, six cementation and alteration phases have been identified: a) micritization, b) mechanical compaction, c) calcitic cementation, d) sparitic cementation, e) microsparitic cementation, and f) chemical compaction. This analysis allowed establishing a chronology of the diagenetic modifications undergone by the carbonates. Results support diagenesis was controlled mainly by tectonics showing major impact in carbonate facies identified at the flexural margin of the rift. The effect would have been linked to exertion of a paleohydrological effect favoring lateral meteoric water migration through faulting. The presence of dolomite in some of the microfacies is linked to the presence of montmorillonite as the dominant Mg-rich-phyllosilicate in clay assemblages most likely acting as the potential source. In turn, Mg is more likely to be replaced by Mn leading to luminescent carbonate microfacies.

Molecular dynamics simulation of thermal, hydraulic, and mechanical properties of bentonite clay at 298 to 373 K

Bentonite, a fine-grained geologic material rich in smectite clay, is considered for use in the isolation of high-level radioactive waste (HLRW) because of its low hydraulic permeability, high swelling pressure, and geochemical stability. A complicating factor in this application is that heat released by nuclear waste can trigger complex coupled thermal-hydraulic-mechanical-chemical (THMC) phenomena within the barrier. Prediction of these phenomena using large-scale simulators, which typically examine problems on scales of 10−2 to 104 m, is inhibited by insufficient knowledge of the material properties of bentonite and their dependence on temperature. Here, these properties were evaluated using replica-exchange molecular dynamics (REMD) simulations of a clay assemblage containing 27 Na-smectite nanoparticles with full atomistic-level resolution solvated using 187,131 water molecules. The simulations yielded predictions of heat capacity, thermal conductivity, thermal expansivity, hydraulic conductivity, and water and ion diffusivity at temperatures of 298 to 373 K. Results showed that temperature modulates the capacity of clay barriers to transfer heat, fluids, and chemical species to different degrees. Material properties of hydrated smectite predicted on scales of tens of nanometers and nanoseconds were consistent with the properties of bentonite measured on scales of centimeters and days.

Comparison of the Late Miocene Sediments and Early Quaternary Red Paleosols in the Penghu Islands, Taiwan and Zhangpu, Fujian

This study aims to compare the clay mineralogy and whole-soil major chemistry of elements in late Miocene soil sediments and early Quaternary red paleosols in the Penghu Islands, (Pescadores), Taiwan, and Zhangpu Volcanic Park, Fujian. There were the late Miocene Chu Wan (CWI and CWII), Shiao Men Yu (SMY) and two intergrade red soils, Chu Wan (CW(irs)) and Shiao Men Yu (SMY(irs)), with three distinctive zones of different dominating kaolins in the profiles of the Penghu Islands. A Tong Wei (TW) paleosol of early Quaternary basaltic eruptions in the Penghu Islands was collected. The Anzei (AZ), Si Yu (HY) and Chianmei (CM) paleosols were sampled from the Penghu Islands and Yulinshi (YLS) paleosols near the Zhangpu Volcanic Park for this study. The CW and SMY paleosols erupted in the late Miocene, and the other paleosols erupted on the Penghu Islands. These paleosols were fractionated into clay fractions and subjected to soil physical and chemical analyses. Kaolin minerals were dominant in the CW(irs) and SMY(irs) paleosols. The top layer (layer one) in the CW(irs) was 7 Å-halloysite, and order/disordered kaolinites were present in layers two and three. The CW(irs) and SMY(irs) hexagonal-like, platy kaolinites (0.1–0.2 µm in diameter), spheroidal and hollow 7 Å-halloysite (layer 1) was determined with transmission electron microscopic (TEM) investigations. The early Quaternary red soil of TW consisted of kaolinite, illite, vermiculite and smectite clay assemblages. Late Miocene paleosols were classified as fine, kaolinite, hyperthermic and Typic Rhodic Paleudults, and the early Quaternary red paleosols were classified as fine, mixed, hyperthermic and Typic Rodistalf, respectively. Late Miocene paleosols contained more clays, lower SiO2/Al2O3 and higher chemical index of weathering (CIW) than early Quaternary paleosols. The kaolin, illite, smectite and vermiculite mineralogy, physical and chemical properties of paleosols and landscapes in the Zhangpu YLS, Fujian, were similar to those of late Miocene sediments and early Quaternary red paleosols in the Penghu Islands.

Climatic and weathering conditions in southern high latitudes during the Turonian-Santonian interval: New insights from IODP Site U1512 (Bight Basin, Southern Australia)

A detailed study, based on a coupled mineralogical and geochemical approach, was done on IODP Site U1512 sediments (Bight Basin, Southern Australia). The mineral assemblages of the clay size fraction (<2 μm), obtained by X-ray diffraction, have been compared to inorganic (major and trace elements) geochemical signals, obtained from both whole rock and clay size fraction, and Sr/Nd isotopes, obtained from clay size fraction to determine climatic and weathering conditions during the Turonian to Santonian interval (∼94–84 Ma, Late Cretaceous) in the southern high latitude band. This study reveals that the mineral assemblages of clay fraction consist of R0-type illite/smectite mixed-layers (considered as smectites), illites, and kaolinites associated with opal-CT and clinoptilolites. Electron microscopy observations have demonstrated a negligible impact of burial diagenesis on clay assemblages while authigenesis contributions of clay minerals are limited and associated with minor volcanic contributions. Clay assemblages would be thus dominantly primary in origin. Based on Sr and Nd isotopic values, clay minerals are interpreted as the resulting from the weathering of rocks and pedogenic blankets of Eastern Australian Highlands and from the remobilization of older sediments from nearby uplifted basins. The chemical compositions of both whole rock and clay size fraction show a relative stability during the studied interval with two exceptions: during the Middle/Late Turonian times for Si, P and Ba and at the Turonian-Coniacian boundary for Ti, K and Zr, associated respectively to an increase of biogenic fraction and to an enhanced input of terrigenous material. The clay assemblages, dominated by smectites, show weak variations along the borehole reflecting stable climatic conditions during the 10-Myr Turonian-Santonian interval. The dominance of smectites, coupled to the absence of chlorite and the low proportions of illite, which are both considered as primary clay minerals, indicates a dominant warm/temperate and sub-humid climate during the studied interval. However, changes in weathering conditions occurred during the Turonian-Santonian interval in southern high latitude. The Early Turonian, characterized by high Chemical Index of Alteration values (>75), is followed by an interval of lower chemical weathering with enhanced biogenic silica during the Middle/Late Turonian. The slight increase of kaolinites, recorded during Coniacian and coeval with increase of Ti/Al and Zr/Al ratios, probably reflects an increase in coarser terrigenous inputs associated with a sea-level fall.

Complexity of clay minerals and its effects on silicon dynamics in hypersaline coastal wetland soils, Brazil

Context Tidal dynamics and high evaporative rates in hypersaline tidal flat (HTF) soils favour a range of clay reactions and the formation of complex clay assemblages. HTFs have a geochemical environment conducive to mineral reactions, and therefore, clay mineral alteration controls essential nutrients in coastal wetlands. Aims The crystallochemical characteristics of clay minerals from two HTFs were studied to provide insights into the complexity of fine clay assemblages in HTF soils and their effects on Si biogeochemistry. Methods The fine clay fraction (&lt;0.2 μm) from these HTFs were investigated using X-ray diffraction (XRD) modelling, XRF, FTIR, TEM–EDS, and silicon sequential extractions. Key results The results have indicated the presence of endmembers and R0 mixed-layered minerals such as kaolinite, smectite, illite, kaolinite–smectite (K–S), kaolinite–illite (K–I), illite–smectite (I–S), and illite–vermiculite (I–V). In general, K–S was the dominant mineral in the samples, occurring in a range of kaolinite layers. Alteration of detrital kaolinite to other mixed-layered minerals occurs in soils, leading to silicon removal from the soil solution because of mineral genesis. There is Mg enrichment at the expense of Al in the samples, and bio-opal appears to be the source of Si for the kaolinite alteration process. Conclusions Our findings indicate that clay authigenesis is an important factor controlling Si dynamics in HTF soils, acting as a sink of Si during the formation of new clay phases. Implications Chemical reactions involving clay minerals are critical for deepening our understanding of the biogeochemistry of wetland soils.

Interaction between Hydrated Smectite Clay Particles as a Function of Salinity (0-1 M) and Counterion Type (Na, K, Ca).

Swelling clay minerals control the hydrologic and mechanical properties of many soils, sediments, and sedimentary rocks. This important and well-known phenomenon remains challenging to predict because it emerges from complex multiscale couplings between aqueous chemistry and colloidal interaction mechanics in nanoporous clay assemblages, for which predictive models remain elusive. In particular, the predominant theory of colloidal interactions across fluid films, the widely used Derjaguin-Landau-Verwey-Overbeek model, fails to predict the ubiquitous existence of stable swelling states at interparticle distances below 3 nm that are stabilized by specific inter-atomic interactions in overlapping electrical double layers between the charged clay surfaces. Atomistic simulations have the potential to generate detailed insights into the mechanisms of these interactions. Recently, we developed a metadynamics-based molecular dynamics simulation methodology that can predict the free energy of interaction between parallel smectite clay particles in a wide range of interparticle distances (from 0.3 to 3 nm) and salinities (from 0.0 to 1.0 M NaCl). Here, we extend this work by characterizing the sensitivity of interparticle interactions to counterion type (Na, K, Ca). We establish a detailed picture of the free energy of interaction of parallel clay particles across water films as the sum of five interaction mechanisms with different sensitivities to salinity, counterion type, and interparticle distance.

Petrography and Clay Mineral Variations Across the Cretaceous/Paleogene (K/Pg) Boundary, Sulaimani, Kurdistan Region, Iraq

The Cretaceous/Paleogene (K/Pg) boundary marks the global extinction of many life forms, this boundary around Sulaimani city coincides with the boundary between Tanjero and Kolosh formations. These two units are flysch deposits of the Zagros Foreland Basin. This study focuses on petrography and clay mineralogy variations between these two units. Petrographic study, X-Ray Diffraction analysis, and Scanning Electron Microscope analysis were conducted on samples from different lithologies. The petrographic study of fine-grain lithologies shows that they are mainly wackestone without variation across the boundary. Sandstone petrography shows variation in framework components by increasing quartz, feldspar, and igneous fragments while argillaceous, carbonates, chert, and chalcedony fragments are decreased from Tanjero to Kolosh formations. Obtained results from XRD and SEM show that the clay mineral assemblage is dominated by corrensite (regularly interstratified chlorite/smectite) with discrete chlorite, smectite and traces of illite. The existence of these clay assemblage suggests that corrensite is the diagenetic product of smectite as it is an intermediate stage of smectite chloritization. Enrichment of precursor smectite and high content of unstable grains in sandstones across the K/Pg boundary is the result of low-intensity weathering in arid and seasonal climates of the source area. The smaller size of detrital smectite than other clay minerals is behind its enrichment in the deep marine basin for both Tanjero and Kolosh formations. Sandstone enrichment with sedimentary fragments in both formations related to uplifted sedimentary terrain in its hinterland, while variation across the boundary indicates gradual uplift of Zagros ophiolite zone in the early Paleogene.

Mineralogy and fluid chemistry controls on lithium isotope fractionation during clay adsorption

Our current understanding of controls on δ7Li variability and fractionation mechanisms is limited, complicating the interpretation of chemical weathering. The role of clay adsorption in Li isotope fractionation during chemical weathering has been confirmed. However, clay assemblage and fluid chemistry are not simple and often variable in weathering settings, potentially modulating Li isotope fractionation on Earth's surface. Here, this research investigated the patterns and processes of Li isotope fractionation during adsorption on kaolinite and smectite with fluid chemistry of 0.001 M NaCl, 0.5 M NaCl, and 0.001 M Na2HPO4. Specifically, the time-dependent experiments with the reaction period up to 15 days revealed that the steady state can be achieved within one day under neutral conditions. The concentration-dependent (initial Li concentration of 2 to 1000 μM) experiments confirmed the accumulation of Li+ in smectite interlayers and adsorption of Li+ only at the external surfaces of kaolinite. Using 0.5 M NaCl solution and the desorption experiments, we hypothesize that outer-sphere Li may exist in the interlayer sites, which can be replaced by excess Na+. In comparison, inner-sphere Li+ (unexchangeable) potentially dominates at the edge surface of clays. The presence of Na2HPO4 increases the binding capacity for Li+ adsorption, in particular for kaolinite. In all cases, 6Li is enriched on clay surfaces and interlayer spaces, consistent with field observations. Fluid chemistry may affect the degree of clay Li adsorption but exerted negligible impacts on isotope fractionation. For kaolinite, a wide variation (up to 30 ‰) in isotopic fractionation between adsorbed and aqueous Li (Δ7Liaq-ad) exists, conforming to a kinetic fractionation mechanism with a constant fractionation factor αad-aq of ~0.992. By contrast, the isotopic fractionation between Li adsorbed on smectite and Li+ left in solutions keeps constant (Δ7Liaq-ad of ~5 ‰), likely following an equilibrium isotope fractionation law with an αad-aq of ~0.995.

Depositional environments and diagenesis of north Gondwana Ediacaran clays (Zenifim and Elat Conglomerate Formations, Israel)

A thick sequence of arkosic sandstones and conglomerates, locally interbedded with volcanic rocks, was deposited in the piedmont region and within intramountain basins of the northern Arabian-Nubian Shield (ANS) during the late Neoproterozoic Ediacaran period. We have studied the geochemistry and clay mineralogy of these sediments in outcrops and drill cores along a ∼200 km long transect in southern Israel, in order to constrain their depositional environments and the diagenetic processes that have affected them. Whole rock trace element data for the Israeli Ediacaran sediments indicates magmatic island arc provenance, consistent with a source in the ANS. Major elements data indicate the importance of pedogenic processes in the source area and modification by grain size sorting during transport and deposition. In the southernmost part of the study area, clay assemblages of the Ediacaran formations include significant proportions of the mineral illite–smectite (I/S), including of randomly interlayered (R0) structure. In the central and northern parts of the study area, the entire Ediacaran section is dominated by illite, while the minor I/S found in this area is always ordered, and changes from R1- to R3-type structure with increasing depth. This transition from R1- to R3-type I/S seems to shallow towards the north. These trends of clay minerals composition along the Ediacaran strata reflect increased paleo-thermal gradient and/or burial depths toward the north, which is correlated with the formation of late Devonian – Carboniferous thermal structure over the Levant area. The pristine, I/S dominated clay assemblage found in the Ediacaran sediments of southernmost Israel is remarkable given these sediments' relatively old age and offers a unique opportunity to probe the Ediacaran climate in this region, which resided at low latitudes at that time. This I/S dominated, kaolinite lacking, clay assemblage, together with relatively low chemical index of alteration values found for the Ediacaran sediments of southern Israel, reflect limited chemical weathering of ANS basement rocks under relatively dry, potentially cool, climatic conditions. The persistence of such climatic conditions within the tropical belt is consistent with a series of late Ediacaran glaciation events, although negating a complete, prolonged 'Snowball Earth'-type global glaciation.

Volume change response and fabric evolution of granular MX80 bentonite along different hydro-mechanical stress paths

Despite the increasing understanding of bentonite behaviour, there is still missing evidence on how different hydro-mechanical loadings, including sequences of hydration and compression, affect the fabric and the volume change behaviour of the material. It is generally assumed that the interplay between the behaviour of clay assemblages and the overall fabric of the material is the reason of having final states that are dependent on the stress path followed. Here the results of an experimental campaign aiming to study these factors are reported and discussed. Free swelling and swelling pressure tests were performed, both followed by compression to a relatively high stress. The experimental program involved various samples that were dismantled at intermediate states in order to perform microstructural observations by means of mercury intrusion porosimetry and electronic scanning microscopy. It was observed that while the void ratio at a given stress level depends on the stress path, subsequent compression led to a unique virgin compression line. The data obtained at the microscale gave further insight for an interpretation of the volume change behaviour observed at the macroscale, showing that at high stress the material tends to recover the same fabric regardless of the path to saturation.

Tectonic and paleoclimatic controls on the composition of inland wetland deposits, Chaco foreland basin, Central Andes

ABSTRACTIn recent decades, the growing interest in wetlands highlights the fundamental role of these complex ecosystems. Integrated sedimentological and geochemical studies that refer to wetlands appear more frequently in the literature, since such approaches provide a window into understanding the functions they have played through geologic time. The Miocene Yecua Formation (Chaco foreland basin, Central Andes, Bolivia) presents sedimentological features that show how siliciclastic, chemical, and biological processes lead to lithofacies and compositional features that are distinctive of wetlands related to back-bulge settings. The succession is composed of shallowing-upward parasequences with various compositional characteristics controlled by tectonic and climatic factors.Data integration obtained from paleocurrents, petrography, and clay mineralogy show the influence of the Central Andes fold and thrust belt located to the west of the basin as a principal source area. The high compositional maturity of sandstones reflects the tectonic control as the main allocyclic variable associated with reworking of already mature sediment sources and transport factors in relation to the distal position of the basin (back-bulge), combined with climatic and paleoenvironmental conditions. XRD and SEM-EDS analyses show that illitic clays represent the main mineral phase of the clay assemblages, and have a detrital origin related to physical weathering processes in the source area. Al-rich smectitic minerals have an authigenic origin and were likely formed by alteration of volcanic detritus as well as from precursor minerals such as illite and feldspars. Kaolinite is determined to be detrital and likely derived from the erosion of floodplains with soil development. Throughout the parasequences, illite–smectite–kaolinite minerals are arranged in different proportions, showing a general vertical trend (from base to top) in which the illitic clays decrease at the expense of the increase in Al-rich smectite and kaolinite. The increase in smectite is accompanied by mixed siliciclastic–carbonate sedimentation, which points to a reduction in the clastic contribution linked to drier conditions. This vertical compositional arrangement reveals a paleoclimatic control, influenced by middle-term wet and dry periods. This work demonstrates that source-rock composition and transport distance (tectonic processes) are the key factors influencing quartz-rich sandstones and illite-rich clay mineral suites in distal positions of continental foreland basins. The long-term tropical to subtropical climate favored the development of inland wetlands and played a secondary role in the final composition of these depositional systems.

Changes in rainfall seasonality inferred from weathering and pedogenic trends in mid-Miocene paleosols of La Tatacoa, Colombia

The authigenic clay mineral assemblage of paleosol profiles and trends in their bulk geochemical evolution provide insight into the intensity of past chemical weathering regimes. These climate-sensitive weathering products can be used to interpret regional changes of the soil moisture regime, which in turn reflects upon the nature of rainfall seasonality (e.g., unimodal vs. bimodal). A conspicuous color change in the overbank deposits and paleosols of the mid-Miocene Honda Group of La Tatacoa, Colombia, is suggestive of a climatic transition which affected the fauna of La Venta - a mid-Miocene fossiliferous site and significant component of the South American Land Mammal Age (SALMA) classification. This study aims to determine how the paleopedology of this region records the climatic transition that modified the annual patterns of rainfall and soil moisture, forcing a change from the gray-colored paleosols hosted by the La Victoria Formation (~13.6 to ~13.1 Myr) to the red-beds of the Villavieja Formation (~13.1 to 12.0 Myr). In the La Victoria profile, the pedogenic fraction of the clay assemblage indicates that vermiculite, chlorite/HIV mixed-layered clays and high concentrations of base cations (Ca2+, Mg2+, Na+) developed in a poorly drained paleosol under reducing (low Eh) and above-neutral pH conditions. By contrast, the presence of kaolinite, goethite and hematite in the red-beds paleosols implies more oxidizing conditions (high Eh), whereas pedogenic vermiculite and smectite suggest a pH close to or mildly below neutral. A common detrital source (parent material) is inferred for both sets of paleosols. However, more intense chemical weathering towards aluminium rich clay in the Villavieja red-bed fossil soils indicates a change in soil humidity from a poorly drained soil environment of a seasonally flooded wetland system to an alternating regime of humidity and drought on a better drained floodplain. The variation in soil moisture is consistent with a change in seasonality from a unimodal rainfall regime in the case of the La Victoria paleosols to bimodal conditions in the case of the paleosols of the Villavieja Fm. After the establishment of a fully glaciated Antarctica and the global climate transition into the Mi-4 glacial stage at ~13.1 Ma, an increased rate of continental weathering along the paleotropical fringe could have been caused by a stronger temperature gradient between the equator and South Pole, shifting the Intertropical Convergence Zone northward and the rainfall patterns with it.

Clay minerals control rare earth elements (REE) fractionation in Brazilian mangrove soils

Mangroves are intertidal tropical ecosystems influenced by marine and terrigenous input. They are important sinks of trace elements, like Rare Earth Elements (REE), which are recognized as excellent indicators of geochemical processes in estuaries. REE data of bulk soil samples from eight mangroves located along the Brazilian coast were correlated with quantitative clay mineral data based on XRD full-profile modelling. Kaolinite has been found to transform to Fe-illite in these mangroves. The clay assemblage was dominated by interstratified phases, including kaolinite-smectite (kaolinite and smectite-rich), illite–smectite and other illitic phases. REE concentrations in bulk soils were LREE > MREE > HREE (where L, M and H indicate light, medium and heavy). Multivariate statistical approach (PCA analysis) using clay mineral concentrations and proxies for relative REE concentrations ([La/Gd]N, [La/Yb]N and [Gd/Yb]N ratios) showed (r > 0.75) that fractionation of LREE over HREE was highest in mangroves where kaolinite, fed with the highly weathered sediments form the Neogene Barreiras Group, was most abundant (67–85% of all clay minerals), while REE fractionation decreased as the relative proportion of Fe-rich smectite increased (26–46 % of all clay minerals). Identified processes of REE control are: 1) Level of sediment weathering within the continent, where higher weathering implies higher kaolinite content and higher REE fractionation (LREE > MREE > HREE); 2) selective leaching of LREE from mangrove soils by saline water; 3) preferential adsorption of HREE by Fe-rich smectite and illite neoformed in the mangrove soils. It is possible to conclude that clay minerals exert an important control on REE fractionation in tropical mangroves.

Million-year-scale alternation of warm–humid and semi-arid periods as a mid-latitude climate mode in the Early Jurassic (late Sinemurian, Laurasian Seaway)

Abstract. Clay mineral and stable isotope (C, O) data are reported from the upper Sinemurian (Lower Jurassic) of the Cardigan Bay Basin (Llanbedr–Mochras Farm borehole, northwestern Wales) and the Paris Basin (Montcornet borehole, northern France) to highlight the prevailing environmental and climatic conditions. In both basins, located at similar palaeolatitudes of 30–35∘ N, the clay mineral assemblages comprise chlorite, illite, illite–smectite mixed layers (R1 I-S), smectite, and kaolinite in various proportions. Because the influence of burial diagenesis and authigenesis is negligible in both boreholes, the clay minerals are interpreted to be derived from the erosion of the Caledonian and Variscan massifs, including their basement and pedogenic cover. In the Cardigan Bay Basin, the variations in the proportions of smectite and kaolinite are inversely related to each other through the entire upper Sinemurian. As in the succeeding Pliensbachian, the upper Sinemurian stratigraphic distribution reveals an alternation of kaolinite-rich intervals reflecting strong hydrolysing conditions and smectite-rich intervals indicating a semi-arid climate. Kaolinite is particularly abundant in the upper part of the obtusum zone and in the oxynotum zone, suggesting more intense hydrolysing conditions likely coeval with warm conditions responsible for an acceleration of the hydrological cycle. In the north of the Paris Basin, the succession is less continuous compared to the Cardigan Bay Basin site, as the oxynotum zone and the upper raricostatum zone are either absent or highly condensed. The clay assemblages are dominantly composed of illite and kaolinite without significant stratigraphic trends, but a smectite-rich interval identified in the obtusum zone is interpreted as a consequence of the emersion of the London–Brabant Massif following a lowering of sea level. Following a slight negative carbon isotope excursion at the obtusum–oxynotum zone transition, a long-term decrease in δ13Corg from the late oxynotum–early raricostatum zones is recorded in the two sites and may precede or partly include the negative carbon isotope excursion of the Sinemurian–Pliensbachian Boundary Event, which is recognised in most basins worldwide and interpreted to signify a late pulse of the Central Atlantic Magmatic Province volcanism.

Compositional variability of regoliths on equatorial highlands (East Timor). Source-rock control and competing effects of weathering and denudation

• Non-mobile elements discriminate Si-rich and Si-poor regoliths formed on distinct rock units. • Si-poor suites tend to be more affected by weathering than Si-rich suites. • Weathering extent better assessed by MIA and α Al Mg in Si-poor regoliths. • Minor alteration and source rock variability compromise weathering assessments in Si-rich suites. • Chemical weathering is strongly limited by high denudation rates. The intensity of chemical decomposition increases with rainfall and temperature, being extreme under equatorial climate, but in tectonically active regions it can be limited by the rapid erosion of surface material when weathering reactions are still incomplete This paper presents mineralogical and geochemical data from weathering mantles exposed on the equatorial mountainous region of Maubisse (East Timor). Two major groups of regoliths, with contrasting Si-content and associated with different parent rocks, are discriminated by non-mobile elements contents. Although partially inherited from parent rock, the geochemistry (e.g., the values obtained for multi-element weathering parameters, such as CIA, CIX, MIAo, WIP, and α-indices of element mobility) and diverse clay assemblages with low kaolinite contents are in general indicative of minor weathering intensities despite wet (>2000 mm of annual rainfall) and warm (annual average temperature ~20 °C) conditions. These compositional data show that weathering reactions are not keeping up with physical denudation in this tectonically active region. Weathering intensity depends on local orographic and lithologic features, being highest on basaltic terranes due to the enrichment in weatherable silicates relative to sedimentary successions. The present research demonstrates the extent to which different factors can control regolith composition in mountainous equatorial regions and how the application of multiple compositional parameters can help to untangle the roles played by those factors.

Geochemistry and mineralogy of Late Carboniferous coal (No. 8) from the Jialequan Mine, Xishan Coalfield, Shanxi Province, China: evidences for the geologic controls of trace elements

Xishan Coalfield is a vital coking coal production base in Shanxi Province of China. This study describes the geochemical, mineralogical, and carbon isotope values of two host rocks and ten coal benches of the Late Carboniferous (No. 8) coal of the Jialequan Mine from Xishan Coalfield. The coals are medium-ash coal (22.42%) and are of bituminous B rank (1.16–1.26%, Ro,ran). Minerals in the No.8 coal are dominated by clay minerals and calcite, along with quartz, pyrite, and anatase. The clay assemblages include kaolinite, illite, and mixed-layer I/S. Sulfate minerals, including bassanite, anhydrite, and jarosite, are identified in several coal benches. The No.8 coal is enriched in Li, Zr, Nb, Hf, Ta, Pb, Th, and U in comparison with world hard coals. Lithium is largely distributed in kaolinite and illite. Zirconium, Hf, Nb, Ta, and Th are related with clay minerals (kaolinite) or anatase if present. Lead dominantly occurs in sulfide minerals, including pyrite/marcasite or water-bearing Fe-oxysulfates, and to a lesser extent in galena. Uranium has an affinity with the carbonate minerals. The ratios of Sr/Ba and redox-sensitive elements indicate an oxic-dysoxic seawater environment during the coal deposition. REY in No.8 coal are related with clay minerals and phosphates minerals, and are derived from the terrigenous input (moyite of the Yinshan Upland), seawater influence, and HREY-rich hydrothermal injection in coal basins.

Post-wildfire denudation assessed from compositional features of river sediments (Central Portugal)

The wildfires of 2017 were responsible for vegetation clearance in a wide area of central Portugal, leaving the weathering profiles more exposed to erosive action. In the present research, suspended loads from a set of catchment areas affected by these fires with diverse geological and orographic features were periodically sampled to evaluate spatial and seasonal variability in sediment production. Bulk mineralogy reflected the geology of the source areas, but displayed high variability even for a single sampling site, which can be partially linked to the grain-size control on sediment composition. Clay mineralogy provided a better picture of the denudation at catchment scale. The predominance of detrital illite with low I5/I10 (ratio of the intensities at 5 Å (002) and 10 Å (001)) indicated very shallow weathering profiles. Chlorite was usually the second most common mineral, more common in metasedimentary-derived sediments, whilst kaolinite was detected only in less steep catchment areas with a predominance of granitic basement rocks or where previous-cycle depositional units are also present. Year-long shifts in clay assemblages were attributed to different spatial patterns of denudation. A depletion of kaolinite occurred in sampling sites mainly sourced by granitoids. An opposite trend was observed where areas with Meso-Cenozoic deposits, less affected by the wildfires than those with basement units, occupy significant proportions of the drainage basins. This trend was ascribed to the wearing out of the weathering profiles covering the basement. Regolith denudation was also testified by a progressive decrease in I5/I10. Shifts in clay mineralogy linked with progressive surface denudation were found to be limited in areas with shallow soils, but may complicate any paleoenvironmental reconstructions based on sediment composition when more evolved weathering profiles have been eroded.