Chemical Weathering Processes Research Articles

Deterioration of volcanic tuffs from rock dwellings in Brhlovce (Slovakia) induced by freeze-thaw cycling studied by non-destructive tests and µCT visualization

The aim of this paper is to evaluate the effect of freeze-thaw-induced weathering of volcanic tuffs from the rock dwellings in the village of Brhlovce (Slovakia) based on a non-destructive and experimental study of tuff pore space properties. Traditional techniques for characterization of the porosity and pore size distribution and new experimental techniques like spontaneous imbibition (pore interconnection) or indicative rock pore structure method (pore size distribution) were compared with pore network models acquired by X-ray computed microtomography before and after freeze-thaw cycling in a custom-built thermodilatometer VLAP04. The results offer insight into how frost weathering altered the pore network of volcanic tuffs. Brhlovce tuffs are highly susceptible to frost damage due to their high porosity, pore interconnectivity, and bimodal pore size distribution pattern, where nanometric-sized micropores predominate over larger micrometric-sized capillary pores. Poromechanical principles were applied to confirm that ice crystallization initiates in well-connected micropores with a corresponding crystallization pressure below 10 MPa. After undergoing 100 freeze-thaw cycles with temperature oscillations ranging from − 10 to 10 °C, there was a significant increase in total porosity, pore interconnectivity, and rock permeability. Additionally, the pore size distribution was altered. These parameters influence the transport of fluids and the moisture regime in rock masses, which can serve as a precursor to physical and chemical weathering processes

Some Geomorphological Implications of Chemical Weathering in Sequences of Sedimentary Rocks in the Kirkuk Structure

This study was based on a review of a group of geomorphological features and characteristics within the Kirkuk anticline in the Low Folded Zone within the Unstable Shelf of Iraq. As well as identifying the role of the chemistry of the rocks that form the geological formations in the studied area and explaining the role of chemical weathering processes in shaping the geomorphological units. Each of these geomorphological units includes several landforms with different lithologies. These shapes were produced as a result of weathering, erosion, and sedimentation processes associated with structural, compositional, rock, and climatic factors. Literature. The exposed rocks in the sedimentation basin, from which different formations are formed, showed variation in their resistance to chemical and physical weathering processes. It has been noted that the chemical weathering of gypsum rocks is of the type of incipient weathering and that of limestone is of the type of incipient to moderate weathering. For the sandstones, they are of the moderate weathering type, while it is noted that the chemical weathering of the claystone and marl is of the extreme weathering type. This demonstrates the important role played by the type of rocks and their chemical composition in highlighting the role of various geomorphological processes in determining the nature of land units and forming the geomorphological features, in addition to the influence of various geological processes and the presence of structural units such as joints, fractures, and faults, as well as the influence of slope and various climatic factors.

Effect of Initial Conditions on the Pore Structure and Bimodal Soil–Water Characteristic Curve of Compacted Granite Residual Soil

Granite residual soil typically forms complex pore structures and exhibits high water sensitivity due to physical and chemical weathering processes. Changes in initial compaction conditions significantly affect the mechanical and hydraulic properties of in situ granite residual soil subgrades, with these variations fundamentally related to changes in pore structure and soil–water characteristics. This study investigates the pore structure and bimodal soil–water characteristic curve (SWCC) of a compacted granite residual soil through laboratory tests and mercury intrusion porosimetry tests. Nine initial conditions were selected based on potential in situ compaction conditions of subgrades, and their effects on the pore size distribution (PSD) and SWCC were thoroughly analyzed. The results show strong correlations between bimodal pore structure and SWCC. The size and volume of inter-aggregate pores exhibit noticeable changes with initial conditions, affecting SWCC within the low and middle suction range. Conversely, the intra-aggregate pores, which constitute over 60% of the pore structures, remain nearly intact across different initial conditions, resulting in similar SWCCs within the high suction range. As the compaction energy increases, the inter-aggregate pores are compressed and lead to a higher water retention capacity. In addition, as the compaction water content increases, the SWCC becomes less sensitive to compaction energy after the aggregates in the pore structure are fully saturated. Additionally, a three-dimensional bimodal SWCC equation is proposed and validated using test data with an R2 value above 0.98. These findings offer valuable insights for the design and quality control of granite residual soil subgrades.

Inherited Grain‐Size Distributions: Effect on Heavy‐Mineral Assemblages in Modern and Ancient Sediments

AbstractHeavy‐mineral suites are used widely in sandstone provenance and are key when connecting source and sink. When characterizing provenance related signatures, it is essential to understand the different factors that may influence a particular heavy‐mineral assemblage for example, chemical weathering or diagenetic processes. Hydrodynamics, causing size‐density sorting, exert major control on the distribution of heavy minerals. Here, we highlight the effect of grain‐size inheritance, essentially the absence of certain grain sizes within a specific heavy‐mineral species, on two distinct types of sediments. Modern deposits from a high‐energy beach in NW Denmark give an analog for heavily reworked sediment, primarily controlled by hydrodynamic processes. In contrast, three Palaeogene turbidite successions in the Eastern Alps were sampled, presenting a more complex history that includes diagenesis. All samples were processed for their heavy‐mineral compositions using Raman spectroscopy, and several techniques applied to determine the effect of grain‐size inheritance. Results show that (a) even within the hydrodynamically well‐sorted beach and placer deposits, evidence of grain‐size inheritance is apparent, and (b) turbidites of variable heavy‐mineral composition show strong effects of grain‐size inheritance for several mineral species. Moreover, considerable intersample contrasts within single turbidite beds are observed. We enforce the importance of understanding grain‐size inheritance, as well as other processes effecting size‐density relations in clastic sediment that go well beyond purely hydrodynamic control of intrasample heavy‐mineral variability.

The role of clay minerals in the concentration and distribution of critical metals in lateritic palaeosols from NE Iberia

The intense chemical weathering processes that lead to the formation of laterites and bauxites result in the enrichment of critical metals (Sc, V, Co, Ga, Ge, Nb, In, Hf, Ta, W, and REEs), which are of great economic interest and are directly involved in the manufacture of various devices essential for the technology transition. This work focuses on combined geochemical and scanning transmission electron microscopy (STEM) studies of lateritic palaeosols developed in continental profiles (Lower Cretaceous, NE Iberia) in order to evaluate the distribution and concentration of critical metals and their possible relationship with weathering processes. In this study, we show that during the process of laterization the highest weathering produces the highest critical metal concentrations (reaching concentrations of 1914.80 ppm in the lateritic palaeosols and 926.30 ppm in the ferruginous macropisoids). Concentrations normalized to the upper continental crust (Taylor and McLennan, 1985) indicate that both the lateritic palaeosols and the macropisoids are enriched in LREEs (256.81 and 223.01 ppm, respectively) and HREEs (107.11and 110.53, respectively). In the lateritic palaeosols, the (La/Sm)c values are higher than those of (Gd/Yb)c, indicating that the LREEs exhibit higher fractionation with weathering, whereas the opposite occurs for the macropisoids, in which the HREEs have higher fractionation. These data indicate that the HREEs are less mobile than the LREEs during laterization. The critical metals present a good positive correlation with Fe, Ti, and Al, but a good negative correlation with K. STEM images and EDS analyses allowed us to identify REE-phases (including monazite, xenotime, and La, Ce and Nd oxides) and nanoparticles of gold adsorbed on the surface of kaolinite crystals. This shows not only that during the laterization process Fe and Ti oxides act as scavengers for the critical metals, but also that kaolinite controls their distribution.

Patterns of distribution of eluvia soils in the oil region of Tatarstan

The article is devoted to the study of eluvial deposits in the southeastern part of the Republic of Tatarstan. As a result of river erosion, a highly dissected and rugged terrain has formed here. Its characteristic elements are erosion-denudation watersheds separated by narrow river valleys and terraced slopes. According to the results of the research, it was revealed that the differences in the structure of weathering profiles in carbonate and terrigenous soil massifs are due to the structural and mineralogical features of rocks that were formed at the stage of sedimentation and subsequent diagenesis. In the central part, on the site of the upper plateau, the rocks underwent mainly physical weathering processes, on the site of the middle plateau – chemical weathering processes, on the site of the lower plateau – physical and chemical weathering processes. Such selectivity in the manifestation of hypergenic processes is due to the predominant lithotypes of sedimentary rocks composing the surfaces of the upper, middle and lower plateaus of the studied territory. Based on the conducted research, the zoning of the studied territory was performed and an engineering and geological map was built. The results obtained made it possible to understand the mechanism of weathering of carbonate and terrigenous rocks, as well as to assess the potential change in their physical and mechanical properties during the construction and operation of buildings and structures.

Regional patterns of zoning hypergenic transformations of sedimentary rocks of the middle Permian age of the Eastern Zakamye

The article is devoted to the study of eluvial deposits in the territory of the Eastern Zakamye. Due to the activity of river erosion, a highly dissected and rugged terrain has formed in this area. Its characteristic elements are erosion-denudation watersheds spaces separated by narrow river valleys and terraced slopes. According to the results of the research, it was revealed that the difference in the structure of weathering profiles in carbonate and terrigenous soil massifs is due to the structural and mineralogical features of rocks acquired at the stage of sedimentation and subsequent diagenesis. In the central part, at the upper plateau site, the rocks underwent mainly physical weathering processes, at the middle plateau site – chemical weathering processes, at the lower plateau site – physical and chemical weathering processes. Such selectivity in the manifestation of hypergenic processes is due to the predominant lithotypes of sedimentary rocks composing the upper, middle and lower plateau surfaces of the plateau of the studied territory. Based on the completed study, the zoning of the territory of the Eastern Zakamye was carried out and an engineering and geological map was built. The results obtained make it possible to understand the mechanism of weathering in carbonate and terrigenous rocks, and, consequently, to assess the potential change in the physical and mechanical properties of rocks, both during construction and during the operation of buildings and structures.

Antimony isotopic fractionation during intensive chemical weathering of basalt in the tropics

This study explored the mechanism of antimony (Sb) isotopic fractionation during chemical weathering and soil biogeochemical processes, which have important implications for Sb isotopic composition in the hydrosphere. We analyzed the major and trace element contents and Sb isotopic composition along an 8 m deep basalt weathering profile in the Huguangyan area of Guangdong Province, southern China. Mineral adsorption experiments were conducted to determine the mechanism of Sb isotopic fractionation in the weathering profile. The following minerals, α-FeOOH, γ-Fe2O3, β-MnO2, γ-Al2O3, montmorillonite-K10, and kaolinite-1A, preferentially adsorbed light Sb isotopes, and increased pH may lead to a lighter isotopic composition of adsorbed Sb. The positive values of τSbTiO2 in the upper profile reflect exogenous Sb inputs, such as rainfall and litterfall. Accordingly, Sb isotopic fractionation is controlled by Sb adsorption onto organic matter and Fe (hydr)oxides in surface soil. At a depth of 1.8 m, Sb and other redox-sensitive elements, such as Fe, Mn, Ce, Co, Cr, and Mo, were distinctly enriched. Changes in the redox conditions result in strong Sb isotopic fractionation. In the middle layer (2–4 m), the combined effects of changes in organic matter content, soil pH, and weathering intensity explains the enrichment of light Sb isotopes. The bottom layer of the profile did not receive exogenous Sb and exhibited an Sb isotopic fractionation pattern similar to that of the basaltic bedrock. In the bottom layer, secondary Fe (hydr)oxides (e.g., goethite and hematite) preferentially adsorb the light Sb isotope (121Sb), whereas the heavy Sb isotope (123Sb) is released into the aquatic environment during intensive chemical weathering.

Groundwater for drinking and industrial purposes: A study of water stability and human health risk assessment from black sand mineral rich coastal region of Kerala, India

Tempero-spatial analysis of groundwater to disseminate the level of drinking water quality and industrial suitability to meet the developmental requirement of a region is a significant area of research. Accordingly, groundwater quality and geochemical interactions prevailed in a black sand mineral rich coastal village is systematically presented in appraisal of drinking and industrial uses for economic engineering purposes. The study area focused is Alappad village, Kollam, Kerala, India has numerous ecological features in a sustainable perspective. The region is unique with placer deposits where an alluvial soil aquifer–saline water–freshwater interaction occurs. This dynamics decides the pertinent hydro geochemistry, potable and designated uses of ground water in season wise. Coastal area is hereby presented based on water quality parameters predicted with the health risk assessment model with a view on human health and cancer risk due to ions (Pb, Ni, Cu, Ba, Fe, Al, Mn, Zn) in groundwater.. To ascertain industrial usage, ground water is evaluated by Langelier saturation index (LSI), Ryznar stability index (RSI), Aggressive index (AI), Larson-Skold index (LS) and Puckorius scaling index (PSI) and inferences are complemented. Chemical weathering and evaporation processes are the natural factors controlling hydrochemistry of this aquifer. This complex coastal system has Nemerow pollution index (NPI) of moderate pollution for total dissolved ions of Fe and lesser for Cu, and Cr present in groundwater. LSI indicates, water is scale forming but non corrosive (46% in PRM, 20% in MON and 47% in POM). Water quality index (WQI) in POM (ranged 28.7–79.9) was excellent for drinking, followed by PRM (23.6–218.2) and MON (33.4–202.7) seasons. This groundwater bears temporary hardness with the dominance of Ca–Mg–HCO3 water type. Health risk assessment of non-carcinogenic risk index of trace metals (Fe, Zn, Mn, and Pb) revealed, children are at ‘low risk’ and ‘medium’ risk with Ni and Cu. The carcinogenic risk index indicated 93% of samples were high Ni induced cancer risk for children, and 87% for adults due to long term ingestion (drinking water intake) pathway. Studies specific on placer mineral deposited coastal region of India are not sufficiently reported with a focus on the above perspectives. Growing need of rare earths for material, device and energy applications, placer mineral explorations can destabilise the coastal hydrosphere. Interrelations of mineral soil – water chemistry prevailed and health hazard predicted would kindle a set of sustainable deliberations. This study summarises the drinking and industrial use of coastal groundwater for future development and human well-being on the basis of quality criteria, corrosion proneness, water stability and health risk factors.

Past and Present Drivers of Karst Formation of Ciénega de El Mangle, Panama

Tropical coastal karst areas represent dynamic, fragile, and biodiverse environments. Central America’s karst regions have been scarcely studied, with most of the research focused on the northern part of the region and on several larger cave systems. The coastal carbonate zones of the Central American region represent a unique karstic landscape, which, so far, has been insufficiently studied. Therefore, in this paper, we aim to describe the (i) landscape geomorphology and (ii) chemical conditions that define Ciénega de El Mangle in Panama as a distinctive karstic site. Carried geomorphological mapping and the characterization of karstic features have resulted in the identification of the different karstic forms and processes that are present within this unique karstic area. Considering that the chosen karstic study area is located in a marine–coastal fringe on the periphery of a lagoon, it is affected by a combination of several factors and processes, including seawater intrusion (through sinkholes), the formation of conchiferous limestone (CaCO3), and NaCl precipitation related to efflorescence. Due to the seasonally humid tropical climate, the chemical weathering processes are intense, thus forming alkaline soils that are hindering the development of mangrove vegetation. The geomorphology of the area results from intense evaporation combined with an influx of brackish groundwater, due to which a landscape has evolved in the marine–coastal strips, of seasonal tropical climates, that exhibit saline beaches, known as a littoral shott. In total, 24 karstic microdolines have evolved within the shott, of which six represent domical geoforms formed by gradual evaporitic precipitation, while seven other geoforms represent active karstic sinkholes filled with brackish water. These results are key for understanding the past and present climate interactions and conditions that have led to the formation of tropical karst environments.

Purple soil inheritance and source of parent rock material and tectonic background in the Sichuan Basin, China

ABSTRACT The parent rock inheritance of the purple soils in the Sichuan Basin is evident, and this is due to factors that are directly related to the parent rocks’ characteristics. Fundamentally, the nature of purple soils is determined by the lithology, chemical composition, weathering, and soil formation of parent rocks, whereas the provenance, and tectonic context of rocks during their diagenesis have a significant influence on their rock attributes. In this study, rocks from four sedimentary layers of the Cretaceous and Jurassic eras – k1c, J3p, J3s, J2s in the Sichuan Basin – as well as the overlying soils were examined, and experimental determinations of the samples’ physical characteristics and chemical elemental composition were made to confirm the parent rock inheritance of purple soils. The essential weathering indices ICV, CIAcorr, WIP, and Na/K were used to study the weathering characteristics of the rocks and soils, and the A-CN-K ternary diagram was used to assess the weathering trends of the rocks. The findings demonstrate that purple soil exhibits significant parent rock inheritance due to its rapid physical soil formation process and weak chemical weathering process. That the rocks of the four sedimentary layers in the study area have all reached a moderate degree of weathering, their original source components are quartzose sedimentary which may have been derived from feldspar source rocks. The tectonic background of the source rocks may be mainly continental arc and active continental margin environment, there may be an oceanic arc tectonic environment.

Provenance of modern sands from Baja California rivers (Mexico): petrographic constraints from light and heavy minerals

ABSTRACT We used high-resolution petrographic and dense-mineral data on modern sand to investigate erosion patterns of the El Rosario, San Fernando, and San Vicente river basins of Baja California (Mexico) to better understand the interrelationships between a complex magmatic arc terrane and surface processes. Modern sand composition of these three rivers reflects the nature of the source region, which lies in the central part of the Alisitos arc (Peninsular Ranges, Baja California, Mexico). The sand detrital modes correspond well with the main structural units drained by the El Rosario, San Fernando, and San Vicente rivers: 1) the Early Cretaceous oceanic arc of the Alisitos Group, 2) the Paleozoic to Mesozoic continental-margin metasedimentary rocks, 3) the Cretaceous plutons, 4) the Upper Cretaceous to Tertiary sedimentary rocks, and 5) the Tertiary volcanics. The modern sand of the San Vicente, San Fernando, and El Rosario rivers is fed chiefly from erosion of a magmatic arc and consists mostly of minor feldspatho-lithic (Fl) to quartzo-litho-feldspathic (qFL) sand and dominant quartzo-feldspatho-lithic (qLF) and litho-feldspatho-quartzose (lQF) sand. Framework petrography also suggests a progressive increase in quartz, K-feldspar, sedimentary and metamorphic lithic fragments, and a decrease in volcanic lithic fragments. Sand, in the Lv field, microlitic (Lvmi), felsitic (Lvf) and lathwork (Lvl) types, and trace amounts of vitric grains (Lvv), such as pumice particles. The andesitic volcanic province of the Alisitos arc sheds quartz-poor sand containing mainly microlitic lithic fragments and plagioclase, whereas sand derived from more felsic rhyolites and rhyodacitic and trachyandesitic products contains largely felsitic volcanic lithics and minor lathwork lithics are mainly derived from subordinate basalts. The abundance of intrusive rock fragments and volcanic and sedimentary lithics of the sampled river sands faithfully represents the relative abundance of a heterogeneous bedrock exposure consisting of sedimentary and metasedimentary rocks, as well as volcanic, plutonic, and medium- to high-grade metamorphic rocks in each drainage basin. Transparent heavy-mineral assemblages including major amounts of amphibole, pyroxene, epidote, titanite, zircon, and minor amounts of staurolite, rutile, actinolite, tourmaline, garnet, kyanite, andalusite, sillimanite, and apatite are in good agreement with a mixed provenance characterized mainly by magmatic, primarily volcanic (andesite, rhyolite, and basalt) and secondarily plutonic (granitoid rocks) and metamorphic source rocks. Some labile species such as hornblende and pyroxene grains show mainly corroded to etched morphologies due to dissolution processes and by chemical weathering processes occurring in a paleo and current semiarid climate. The Zircon+Tourmaline+Rutile index of the heavy-mineral modes, coupled with their subrounded to rounded grain surface texture, indicates recycling from the sedimentary source rocks. Heavy-mineral abundance and weathering textures in the San Fernando and San Vincente river sands match predominantly volcanic bedrock lithologies, while the El Rosario river sands match sedimentary and metasedimentary source rocks.

Using hydrogeochemical facies and signatures for groundwater characterization and evolution assessment in aquifers with contrasting climate and geology in Tanzania

This study aimed at characterizing groundwater evolution using hydrogeochemical facies and signatures in two basins with contrasting climate and geology, one in the central part and the other in the eastern coast of Tanzania. The Kimbiji (humid, unconsolidated) aquifer is covered by an unconfined layer in the upper parts and a confined layer in the lower parts, with strong artesian flow characteristics while groundwater in the Singida (semi-arid, consolidated) aquifer occurs in weathered shallow layers and in fractures of basement rocks. Fieldwork involved water sampling from precipitation, deep and shallow boreholes, springs and surface water from rivers and lakes in the two study areas. These were specifically conducted for hydrogeochemical analyses to unravel hydrogeochemical facies and signatures in the two aquifers. Physico-chemical water quality parameters [i.e., pH, electrical conductivity (EC) and total dissolved solids (TDS)] were measured in situ using HANNA HI 9829 Multiparameter Analyzer. Standard procedures for water sampling, preservation, transportation, and chemical analyses of major ions were conducted as documented in previous studies. Samples were carried and stored at 4 °C prior to their shipping and analyses at Water analysis and testing in environmental regions (WATER) laboratory in Iringa, Tanzania. The mechanism controlling groundwater geochemistry were revealed by assessing the reactions between groundwater and aquifer minerals. Chloro-Alkaline indices (CAIs) were used to study cation exchange processes between the groundwater and its host environment at stagnancy and/or during groundwater travel. The Gibbs ratio 1 values were found to range from 0.26 to 0.94 and Gibbs ratio 2 values ranged from 0.11 to 0.95. The majority of the samples irrespective of the contrast in climate and geology were observed to fall in the rock–water interaction zone. This is attributed to chemical weathering processes where the dissolution of rock forming minerals takes place. Some samples exhibited replacement of Na+ by Ca2+ or Mg2+ (S18), loss of Na+ through precipitation of evaporate rocks (S11, S13, S16, S19), and water flowing through crystalline rocks (S1, S2, S4, S6, S8, S10, S12, S13, S14, S21). The ratio Na+: Ca2+ > 1.0 (S1, S4, S8, S10, S12, S14, S17, S18, S19, S21) explains base ion exchange while the ratio < 1 implies a reverse ion exchange (S2, S6, S11, S13, S16).The Ca2+: SO42− + HCO3− ratio < 1.0 connotes groundwater flowing through a normal hydrological cycle (S1, S4, S8, S10, S12, S14, S17, S18, S2, S6, S11, S13, S21) and a ratio greater than 1 is an indication of Ca2+–Cl− brines (S16, S19). The HCO3−: Cl− hydrogeochemical signatures divided the Singida aquifer into upper water flow course, where groundwater recharge occurs (S52, S54, S56, S57, and S58) and the discharge zone, (S53, S59, S60, S61) which is a lower groundwater flow course. Interestingly, the Mg2+ + Ca2+: Na+ + K+ ratios as well confirmed that the Singida aquifer is a lower groundwater flow course (discharge zone). The greater than 1 Na+: Ca2+ ratios confirm the dominance of base ion exchange in the Singida aquifer as it has been explained by the CAIs and the Piper diagram. The Gibbs diagrams revealed that the hydrochemistry of groundwater in the Kimbiji and Singida aquifers are mainly in the rock weathering region, affirming that there is high dissolution with rock forming minerals. This is thus one of the main controls of groundwater mineralization in the two study areas. The similarity of hydrogeochemical signatures between a distant surface water body, Lake Inkhanoda and Mwankoko borehole in the Singida aquifer is an indication that there is a discernible interaction between groundwater and surface water, further revealing that the Singida aquifer is fed by sub-regional and regional groundwater flow systems.

Holocene sediment source analysis and paleoclimatic significance of core KZK01 from the eastern part of the Beibu Gulf

Identifying the sources of sediments is of great significance in reconstructing Holocene paleoclimate evolution in the Beibu Gulf and in understanding the characteristics of regional responses to changes in global climate. The Holocene paleoclimatic evolutionary history of the Beibu Gulf was investigated by chronological, geochemical, and mineralogical means using the sediments of Core KZK01 from the eastern part of the Beibu Gulf. The rare earth element (REE) distribution curves, (Gd/Yb)N and (La/Yb)N discriminant diagram, and (Gd/Lu)N and ∑LREE/∑HREE discriminant diagram indicated that the detrital materials in the eastern part of the Beibu Gulf primarily originated from Hainan Island and its proximal sources, with considerable contributions from Taiwan and Pearl River materials. Source analysis of clay minerals showed that Luzon Island was the main source of smectite, followed by Hainan Island. Rivers in Taiwan were the main sources of illite in the study area, followed by the Red River. The Red River was the main contributor of chlorite, followed by the Pearl River. Kaolinite mainly originated from Hainan Island and Guangxi. Coastal currents, surface currents, and warm currents were the main drivers of material transport. Paleoclimatic variations since the Holocene in the Beibu Gulf were divided into three stages: 12–9 cal kyr BP, 9–1.3 cal kyr BP, and 1.3 cal kyr BP to the present. During different stages of climatic evolution, drought was often accompanied by cold and humidity coexisted with warmth, and cold-dry-warm-humid alternation is characterized by significant phases. The illite crystallinity clearly recorded the extreme cold events, such as Bond Events (except Bond6) and the Younger Dryas, and the change trend was essentially consistent with the regional climate record, reflecting the control of global climate change on the process of land–sea interaction in the tropical region. Furthermore, it highlights the great potential of illite crystallinity as a proxy indicator for reconstructing the surface chemical weathering processes of the region.

Lithium partition and isotopic fractionation for cation exchange in clay: Insights from molecular simulations

Chemical weathering is one of the most important processes on the Earth’s surface, and lithium isotopes have been used as a promising tracer of silicate weathering, as the secondary clay minerals precipitated during silicate weathering are thought to preferentially incorporate the lighter 6Li isotope. However, to utilize lithium isotopes as a geochemical tracer, it is essential to quantitatively understand the partitioning of Li in clay minerals, including structurally bound Li and exchangeable interlayer ions, as well as the associated isotope fractionation. With classical molecular dynamic simulations and thermodynamic calculations, the cation exchange between Na-/K-montmorillonite and solvated Li in environmental solution are disclosed under different aqueous activity conditions. The Li+ ion, whose hydration ability is stronger than Na+ and K+ ions, is easier to swell the montmorillonite and shows less affinity for the clay. And the calculated cationic selectivity coefficients between Na+/K+ and Li+ ions are Kc (Li → Na) = 2.0, Kc (Li → K) = 10.0 for Arizona-type montmorillonite and Kc (Li → Na) = 1.0, Kc (Li → K) = 4.0 for Wyoming-type montmorillonite, which are comparable to reported experiments. The cationic partition of Li in the clay interlayer decreases when the hydration states of montmorillonite transform from triple-layer to bilayer and then to monolayer. Based on the density functional theory, the Li isotope fractionations for Li in clay interlayer sites and structural octahedral sites are further derived by thermodynamic calculations with path integral molecular dynamic simulation, which deals with the quantum anharmonicity. The behaviors of Li isotope in the bilayer hydration state closely resembles that in the aqueous solution, and only a slight Li isotope fractionation is found between the monolayer hydrated octahedral-substituted clay and solution phase (Δ7Limonolayer-aq = −2.0‰). While Li isotope fractionation between aqueous solution and mica structural sites is significant (Δ7Listructural-aq = −10.4‰) and shows an obvious quantum anharmonicity, which indicates the importance of the anharmonic treatment for Li isotope fractionation calculations. The newly calculated Li equilibrium isotope fractionation between clay and aqueous solution deviates from the experimentally determined fractionation factor, which can be attributed to the kinetic effects. Moreover, on the basis of the surface kinetic reaction model, the Li isotope fractionation becomes more pronounced with higher clay growth rate. By integrating the cationic selectivity coefficient and Li isotope fractionation, it is possible to constrain the fluid composition during Li-clay deposit and diagenesis, and to evaluate the intensity of chemical weathering processes as well as the related carbon cycle.

Characteristics of hydrochemical and stable isotopes in the Upper and Middle Reaches of the Yarlung Tsangpo River

There have been few studies on the spatiotemporal variation of the hydrochemistry and stable isotopes characteristics in the upper and middle reaches of the Yarlung Tsangpo River owing to its high elevation and alpine climate, and the primary controlling mechanisms have yet to be clarified. Statistical analysis, a Piper diagram, Gibbs diagrams, ion correlation analysis, and other methods were integrated to analyze water samples from the main stream and tributaries of the Yarlung Tsangpo River together with rainwater samples from certain areas obtained in May 2020. And both the formation mechanism of the hydrochemistry and the process of chemical weathering were explored. The results revealed that river water in the basin was of HCO3−–SO42−–Ca2+ type (i.e., weakly alkaline), evaporite weathering had little impact on chemical weathering in the upper and middle reaches of the Yarlung Tsangpo River, and chemical weathering in the basin was controlled jointly by weathering of silicate rock and carbonate rock. Overall, the mean value of deuterium excess of the samples from the upper and middle reaches of the Yarlung Tsangpo River was 7.22‰, i.e., lower than the global mean of precipitation (10‰), indicating that the sampled water was subject to evaporation enrichment to some extent. Owing to the unique climatic and geographic conditions of the Qinghai–Tibet Plateau, the upper and middle reaches of the Yarlung Tsangpo River were also affected by water–rock interaction (chemical weathering and physical erosion). In addition, the relationship of stable isotopes between rainwater and riverwater also suggested that precipitation is an important source for river water in the upper and middle reaches of the Yarlung Tsangpo River.

Chemical weathering detection in the periglacial landscapes of Maritime Antarctica: New approach using geophysical sensors, topographic variables and machine learning algorithms

The chemical weathering intensity in Antarctica is underestimated. As the chemical weathering intensity increases, hydrological, geochemical and geophysical changes occur in the different environmental spheres and at their interfaces through reactions and energy flows. Thus, once chemical weathering rates are understood and estimated, they can be used to predict and assess changes and trends in different environmental spheres. Few studies on the chemical weathering intensity have been performed in Antarctica. We used radiometric and magnetic properties associated with terrain attributes and the chemical degree of alteration of the igneous rock to model the chemical weathering intensity in Maritime Antarctica by using machine learning. Then, we related the chemical weathering intensity and geophysical variables with periglacial processes. To do this, gamma-spectrometric and magnetic readings were carried out using proximal-field sensors at 91 points located on different lithologies in a representative area of Maritime Antarctica. A qualitative analysis of chemical alteration for the different lithologies was carried out based on field observations and rock properties, and the levels of the chemical weathering degree were established. The geophysical data associated with terrain attributes were used as input data in the modeling of the weathering intensity. Then, the levels of the rock weathering degree were used as the “y” variable in the models. The results indicated that the C5.0 algorithm had the best performance in predicting the weathering intensity, and the most important variables were eTh, 40K, 40K/eTh, 40K/eU, the magnetic susceptibility and terrain attributes. The contents of radionuclides and ferrimagnetic minerals in different lithologies, concomitantly with the intensity at which chemical weathering occurs, determine the contents of these elements. However, the stability and distribution of these elements in a cold periglacial environment are controlled by periglacial processes. The chemical weathering intensity prediction model using gamma-spectrometric and magnetic data matched the in situ estimate of the chemical degree of alteration of the rock. The pyritized andesites showed the highest intensities of weathering, followed by tuffites, diorites, andesitic basalts and basaltic andesites, and the lowest weathering intensity was shown by undifferentiated marine sediments. This work highlighted the suitability of using machine learning techniques and proximal-field sensor data to study the chemical weathering process on different rocks in these important and inhospitable areas of the cryosphere system.

Lithological control on the formation of ferruginous duricrusts in the Espinhaço Range (Minas Gerais, Brazil)

The Espinhaço Range is the scene of a long history of exposure to chemical weathering and erosion processes since the Cretaceous. As a result, ferruginous duricrusts can be considered as the fingerprint of the long-term surface process and may provide us critical clues about changes in paleo-environmental features during the Cenozoic. In addition, specifically for the Diamantina plateau, located in the state of Minas Gerais (Brazil), there is great interest in studying the duricrusts of the Espinhaço Range, because they are associated with diamond mining, explored since the eighteenth century and which gave its name to the region. Even so, few studies have contributed to understanding their formation and morphological diversity. Mineralogical, geochemical, and micromorphological studies were undertaken to understand the processes involved in the formation of the two representative types of ferruginous duricrust, linked to phyllites of Espinhaço Supergroup: platy and massive types. The platy duricrust develops from the weathering of a banded ilmenite-hematite phyllite where the alteromorphization of its compositional banding and original foliation leads to the formation of an isalteritic duricrust. The massive duricrust, associated with diamond mining, is genetically linked to a quartz-phengite phyllite. Both duricrust profiles show relative enrichment in Fe and P and depletion of the other major elements compared to the saprolite, however, the iron concentration was 10 times greater in the massive than the platy duricrust. The REEs show similar distribution patterns with preferential leaching in both duricrusts. The compositional and textural variation of the phyllite in the Diamantina Plateau leads to the distinct evolution of two representative duricrusts profiles. The mineralogical, micromorphological, and geochemical analyses reinforce the lithological control in the formation of these two different types of ferruginous duricrusts in the study area, located in similar topographic and climatic conditions.

Magnetoclimatological Record of Late Pleistocene Loess in the Southern Hunshandake Sandy Land, Inner Mongolia: A Threshold Response to the East Asian Summer Monsoon Variations

AbstractWe report the first complete loess–paleosol record spanning the last 130 kyr from the southern extremity of the Hunshandake Sandy Land (HSL) in central‐eastern Mongolia. Our combined mineral magnetic and geochemical results demonstrate that during the last interglacial, the front of the East Asian summer monsoon (EASM) extended to central‐eastern Inner Mongolia, consistent with modern observations of climate change. However, during the last glacial, typical magnetic parameters (e.g., magnetic susceptibility and anhysteretic remanent magnetization and their ratios), which have been successfully adopted to denote the EASM variations on the Chinese Loess Plateau (CLP), show only muted temporal variations and cannot be readily correlated with equivalent records from the main body of the CLP. Remarkably, the Zr/Rb ratio, a robust geochemical indictor of the winter monsoon, is positively correlated with saturation isothermal remanent magnetization and saturation magnetization during the last glacial, demonstrating the strong control of wind vigor on high‐field magnetization signals dominated by lithogenic ferrimagnetic minerals. In contrast to the variable response of magnetic parameters to regional paleoclimatic fluctuations, the Rb/Sr and Ba/Sr ratios (two summer monsoon indicators) faithfully track weak chemical weathering processes and fine‐scale monsoon oscillations, especially during the last glacial. Additionally, we found that higher proportions of pedogenic high‐coercivity magnetic minerals were formed during the last interglacial, which may reflect relatively low rainfall but higher evapotranspiration in the southern extremity of the HSL compared with the CLP. We therefore attribute this complex magnetic record to a threshold response to the EASM variations in eastern Inner Mongolia.

Chemical weathering of small watersheds in the upper reaches of Jinsha river on the eastern edge of the Qinghai–Tibet Plateau

Land chemical weathering is a crucial and common geological process on the Earth’s surface. Studying the surface chemical weathering process in basins is important to the net consumption rate of atmospheric CO2, climate change in geological history, and the global carbon cycle. In this study, a small watershed in the upper reaches of Jinsha River on the eastern edge of the Qinghai-Tibet Plateau is selected as the study area. By measuring the physical and chemical properties and the main ion content of the water in the watershed and by using the factor analysis method, the source of the main ion components in the water in the alpine basin and the characteristics of the chemical weathering of the basin rocks are examined. Results show that the pH value of surface water in the study area varies from 7.4 to 8.2, and the overall performance is moderately to weakly alkaline. The total salinity in the basin is between 52.42 and 398.19 mg/L, with an average value of 180.06 mg/L. The concentration of main cations in surface water follows the order Ca2+>Mg2+>Na+>K+. The concentration relationship of the main anions is in the order HCO3−>SO42−>Cl−, and the hydrochemical type is HCO3_Ca. The main source of ions in the study area is rock weathering, which is controlled by the chemical weathering of carbonate rocks. The contribution rates of carbonate (mainly dolomite and calcite dissolution), evaporite, and silicate to the dissolved matter in the river are 59.40%, 7.30%, and 3.00% respectively, and the contribution rate of CO2 in the atmosphere to the dissolved matter in the river is 30.30%. The total chemical weathering rate in the study area is 29.09 t/km2 ⋅a, which is at a low level, indicating that weak hydrothermal conditions slow down the chemical weathering process of rock minerals.