Chemical Index Of Alteration Research Articles

Fractionation Mechanism and Flux Estimation of Strontium Isotopes During Basalt Weathering

AbstractThe fluxes of metal cations and isotopes released by weathering of silicate rocks are crucial and a prerequisite for constraining geochemical fluxes to rivers and oceans. This study presents mineral and elemental compositions along with 87Sr/86Sr and δ88Sr data from a basaltic weathering regolith on Hainan Island, South China to elucidate Sr isotope fractionation and weathering fluxes. The 87Sr/86Sr ratios vary from 0.703936 to 0.706338 as a result of differential weathering of the minerals. δ88Sr values in the weathering regolith range from −0.29 to 0.37‰, with the majority of the weathering regolith having lower δ88Sr values than the parent rock. Sr is leached into the soil solution during plagioclase decomposition, while 86Sr is preferentially adsorbed on the surface of secondary minerals. As weathering progresses, smectite decomposes and kaolinite desorbs under weakly acidic conditions, releasing the previously adsorbed 86Sr into the soil solution. The differential weathering of kaolinite and smectite controls the δ88Sr values of the weathering regolith, with pH being an important determinant of isotope fractionation. Furthermore, Sr elemental fluxes (SrFlux) and Sr isotopic fluxes (δ88SrFlux) of this weathering regolith were calculated using a mass balance model, yielding mean values of 0.20 (mg cm−3 Myr−1) and 0.052 (‰ (mg cm−3 Myr−1)), respectively. The δ88SrFlux exhibits a nonlinear positive correlation with the Chemical Index of Alteration (CIA), indicating that enhanced weathering leads to significant stable Sr isotope fractionation at CIA values below 95%. Our research promotes the understanding of Sr recycling and the fractionation behavior of stable Sr isotopes during consecutive weathering.

Geochemical indicators to constrain weathering, provenance and tectonic setting of the Pisha Sandstone (Early–Middle Triassic) in Northeast Ordos Basin, China

The Pisha Sandstone is widely exposed in the northeastern margin of the Ordos basin. Since the Mesozoic the basin was subjected to uneven uplift several times, strong weathering and erosion have been occurring and a large amount of sediments derived from these erosional strata are input into the lower Yellow River, posing a fragile ecological environment along the river. However, the geochemical characteristics of the Pisha Sandstone have remained poorly understood. In this study, we focus on the Pisha Sandstone from Early–Middle Triassic Liujiagou, Heshanggou and Ermaying Formation, present a very first petrographic and geochemical data together with detailed field geological characteristics, aiming to place geochemical indicators on weathering, provenance and tectonic setting of the Pisha Sandstone. The results show that sandstones in Pisha Sandstone are classified as arkose, litharenite and wacke. The geochemical proxies including Chemical Index of Alteration (CIA = 67.2), Chemical Index of Weathering (CIW = 80.1), Plagioclase Index of Alteration (PIA = 75.6) and Index of Compositional Variability (ICV = 1.6) indicate Pisha Sandstone experienced first–cycle deposit and moderate to strong chemical weathering. Trace element and rare earth element concentrations together with their ratios (La/Sc, La/Co, Th/Sc, Th/Co, Cr/Th) reveal a felsic provenance, and source rock compositions are predominantly granodiorite and granite from the north margin of the Inner Mongolia Paleo–Uplift (IMPU), with a small amount of mafic or intermediate components. The geochemical signatures and tectonic discrimination diagrams display a collision setting for the Pisha Sandstone and further reveal the sediments had been deposited in a continental island arc setting. The results of this work may provide new theoretical basis for environmental protection in the Pisha Sandstone area.

Carboniferous–Early Permian volcano-sedimentary units from the northern margin of the North China Craton recorded subduction initiation in the Paleo-Asian Ocean

The precise timing of subduction initiation of the Paleo-Asian Ocean (PAO) in the northern margin of the North China Craton (NCC) remains controversial. In this study, we have conducted zircon UPb dating, whole-rock major and trace elements, and zircon Hf isotope analyses on metadacites and metamorphic greywackes from the Changde volcano-sedimentary rocks, feldspar quartz sandstones and argillaceous siltstones from the Luquantun Formation and the Sidao sedimentary rocks in central-eastern Jilin Province (NE China), to constrain the initial closure of the PAO. We obtained Early Carboniferous zircon UPb ages (345 ± 2 Ma and 351 ± 7 Ma) from the Changde volcano-sedimentary rocks. The metadacites are characterized by the enrichment in light rare earth elements and large ion lithophile elements, depletion in heavy rare earth elements and high field strength elements, and rare earth element ratios similar to those of the continental crust, indicating that these rocks originated from crustal melting. The metadacites exhibit affinity with the peraluminous A-type granite, with high zircon εHf(t) values (+3.46 − +12.21) and TDM2 of 1132–571 Ma, suggesting that they formed in a post-collisional extensional setting. Detrital zircon UPb ages from the Luquantun Formation and Sidao sedimentary rocks constrain their maximum depositional ages to the Late Carboniferous (319 ± 5 Ma) and Early Permian (284 ± 4 Ma), respectively. Most detrital zircons have age peaks at 1800 Ma with negative zircon εHf(t) values, and 2500 Ma with positive zircon εHf(t) values, suggesting that the Carboniferous–Early Permian sediments from these two formations were mainly sourced from the NCC. Moreover, the chemical index of alteration, index of compositional variability, and plagioclase index of alteration values suggest that the sediments of the Changde volcano-sedimentary rocks originated from a mafic igneous source with a low degree of weathering and a sedimentary recycling history, while the samples from the Luquantun Formation and Sidao sedimentary rocks were sourced from an intermediate-felsic igneous rock with a moderate to intense degree of weathering and mainly influenced by source composition. The crystallization age curves and summary plots of detrital zircons indicate that the Early Carboniferous metamorphic greywackes from the Changde Formation were mainly deposited in a passive margin, while the Carboniferous–Early Permian sediments of the Luquantun Formation and Sidao sedimentary rocks were mainly deposited in an active margin. We suggest that the tectonic transition from passive to active margin occurred at ∼333 Ma, marking subduction initiation in the PAO close to the northern margin of the NCC.

Formation mechanisms of fluvial residues from eastern watersheds of China: Insights from corrected weathering process and sediment provenance

Investigating the weathering process and provenance of fluvial residues plays a crucial role in revealing superficial circulation on earth. Although the transfer and inheritance processes have been well elaborated for intra-watersheds, the limitations and applications of geochemical proxies need to be further explored for cross-watersheds. Geochemical analysis was performed on 541 surficial sediment samples from 12 intertidal zones in China, combined with traditional weathering indices, mass transfer coefficients, and rare earth element parameters, to gain a better understanding of their geochemical behavior. Based on the interactions of lithology, hydrodynamic sorting, and sedimentary recycling on various weathering indices, the metamorphic and succession processes of the residues were fully characterized during the source-to-sink process. The weathering index of Parker (3.9–66.2) was more susceptible to the hydrodynamic sorting effect, whereas the chemical index of alteration (45.8–83.9) was heavily influenced by the sedimentary recycling process. In comparison, the mass transfer coefficient of Na provides better performance in the early weathering stage and is optimally protected from the effects of hydrodynamic sorting and sedimentary recycling. As confirmed by the corrected mass transfer coefficients and weathering indices, regional temperature and precipitation co-dominated the weathering heterogeneity. Parameters excluding heavy rare earth elements were hardly affected by the weathering process and grain-size effect, and were the most sensitive geochemical proxies for tracing the provenance of fluvial residues. This could provide a scientific basis for cross-watershed research, source apportionment, and regional geological background.

The Lanseria palaeosol: Implications for palaeoweathering and terrestrial life at ∼2.6 Ga on the Kaapvaal Craton

Archaean palaeosols are a rare record of surface processes on the early Earth. We report on the discovery of a palaeoweathering profile developed at the contact between Mesoarchaean basement and the Neoarchaean to Palaeoproterozoic Transvaal Supergroup along the northern margin of the Johannesburg Dome, Kaapvaal Craton. Granodiorite ∼3.1 Ga old was subjected to weathering just prior to the deposition of the ∼2.6 Ga Black Reef Formation. The ∼25 m-thick profile is dominated by a palaeosaprolite and organic matter-rich palaeosol remnant at the top that experienced erosion upon marine transgression on the Kaapvaal Craton. The Al concentration of the profile, sericite content and chemical index of alteration (CIA) values progressively increase from the parent granodiorite towards the nonconformity as Fe, Mg, Na and Ca concentrations decrease. The decrease of Co and Zn together with Fe and the retention of U, V and Cr collectively suggest a reducing and acidic environment at the time of weathering. Carbonaceous matter with negative δ13C isotopic values (−27 to −23 ‰V-PDB) in the palaeosol is compatible with the former presence of photoautotrophic microbes. Copper depletion and mobility of P may indicate the presence of organic acids that enhanced chemical weathering of the bedrock. The palaeoweathering profile was subjected to diagenetic-hydrothermal K-metasomatism, regional metamorphism and deformation, which collectively transformed the regolith into a quartz-sericite schist, as it presently occurs. Despite these modifications, the original record of palaeoweathering and microbial colonisation is well preserved. Colonisation of a large swath of the Kaapvaal Craton by terrestrial soil-dwelling microbiota at 2.60 Ga is recorded in abundant soil-derived carbonaceous matter in transgressive marine conglomerates that erosively overlie the palaeosol.

Chemical weathering along a one-million-year soil age gradient on the Galápagos Islands

The Galápagos archipelago, a chain of islands formed by hotspot-induced volcanism on the Nazca tectonic plate, exhibits pronounced gradients of rock age and climate. Here, we investigate chemical weathering along a soil chronosequence (1.5 to 1070 ka) and under humid vs. dry conditions. Our results show considerable loss of base cations already in the early to intermediate phases of weathering under humid conditions (e.g. 95 % of Na and 78 % of Mg lost from the topsoil after 26 ka) and almost complete loss from the entire profile in soils older than 800 ka. Depletion of Si was less pronounced, with topsoil losses of 24 % and 63–68 % after 26 ka and >800 ka, respectively. Under dry conditions, weathering rates were much lower, e.g. 33 % of Na and 1.4 % of Mg lost from the topsoil after 26 ka. Indices of chemical weathering, e.g. the Chemical Index of Alteration and the Ruxton Ratio, correlated well with indicators of pedogenic development, such as solum thickness, soil pH, or the ratio of oxalate- to dithionite-extractable Fe. Total weathering flux and associated CO2 consumption rates estimated from profile-scale element losses in this study exceeded catchment-scale estimates reported for other volcanic islands or global averages during the early weathering phase, but were much lower in the intermediate and late phases. Nevertheless, total C drawdown was dominated by soil organic C sequestration (70–90 % share) rather than inorganic, weathering-induced CO2 consumption during early pedogenesis (≤4.3 ka), and the relative importance switched in the intermediate and late phases (90–95 % share of weathering-induced C drawdown at ≥166 ka). Dust deposition derived from a nearby ocean sediment core was <20 % of total basalt mass loss at the young and intermediate-aged sites, but reached 40–60 % at the older sites (>800 ka). Our results suggest that (1) young volcanic surfaces are very efficient (inorganic and organic) C sinks, (2) the development of thick soil covers at advanced pedogenic stages effectively shields the underlying rocks and decelerates weathering, and (3) dust inputs become an increasingly important biogeochemical factor in such highly weathered environments.

Weathering Intensity, Paleoclimatic, and Progressive Expansion of Bottom-Water Anoxia in the Middle Jurassic Khatatba Formation, Southern Tethys: Geochemical Perspectives

The Jurassic Period was a significant phase of variable organic matter accumulation in paleo-shelf areas of the southern Tethys (Egypt). Reconstructing the paleoredox conditions, paleoclimate, and weathering intensity, along with the role of terrigenous sediment flux and mineralogical maturity, is important for understanding basin infill history and prevalent paleoenvironmental conditions. Here, inorganic geochemical data are presented from the Middle Jurassic Khatatba Formation and two samples from the underlying Ras Qattara and the overlying Masajid formations in the Jana-1x well, Shushan Basin, Western Desert. Twenty-four (24) whole-rock samples were analyzed for their major and trace element composition and carbonate content. The Khatatba Formation represents one of the major hydrocarbon source rocks in the North Western Desert, Egypt. Redox conditions were assessed based on enrichment factors of redox-sensitive elements Mo, V, U, and Co. Results revealed that the Khatatba Formation was deposited under predominant anoxic bottom and pore water conditions, in contrast to the oxic settings that were prevalent during the deposition of the Ras Qattara and Masajid formations. Continental weathering intensity and paleoclimate were reconstructed based on several proxies, such as the chemical index of alteration (CIA), K2O/Rb, Rb/Sr, Ln(Al2O3/Na2O), and Al/K ratios, indicating that the studied succession was deposited during alternating phases between weak and moderate weathering intensity under arid and warm-humid climates, respectively. Periods of enhanced continental weathering were associated with high values of clastic ratios such as Si/Al, Ti/Al, and Zr/Al, suggesting increased terrigenous sediment supply during intensified hydrological cycling. These ratios further provided inferences about the changes in sediment grain size, such as a change from shale to coarse silt- and sand-size fractions.

Controls on the formation of Mn carbonates in mudrocks of the Datangpo Formation, Northern Margin Rift Basin, Yangtze Block

Deglaciation following the Sturtian Ice Age led to widespread manganese carbonate precipitates within marine mudrocks, reflecting unique climatic and oceanographic changes. The Mn carbonates hold economic importance in the Datangpo Formation, Yangtze Block, South China. Although their genesis in the Nanhua Rift Basin is well understood, little is known regarding their formation mechanism in the North Margin Rift Basin (NMRB). With growing interest in Mn ore exploration in this region, this study examines the weathering trend, climate patterns and watermass conditions using a variety of geochemical proxies. The results reveal two phases of climate variation during the deglaciation. Climate during the early phase (Phase I) was unstable, characterized by fluctuating values of Chemical Index of Alteration (CIA = 65 ± 4) and elevated Li isotope (8.8 ± 3.0‰) patterns. The degree of chemical weathering during the later stage (Phase II) was relatively stable (CIA = 65 ± 1, δ7Li = 5.4 ± 2.7‰), but the weathering intensity increased due to the reduced denudation rate, possibly related to a shift in the basin development. Fe speciation data indicate euxinia prevailing much of the section. However, Mo and U enrichment (> 1) and fluctuating ratios of Mo versus total organic content (0–40) suggest that pulses of freshwater influx associated with climate variation during Phase I caused the fluctuation of the chemocline along the continental shelf, facilitating the formation of Mn carbonates through the particulate Fe-Mn-hydroxide shuttle. With the establishment of stabilized climate, basin tectonics, and watermass circulation during Phase II, the accumulation of Mn carbonates in the sediments became less significant. The accumulation of Mn carbonates in the NMRB conforms to the “bathtub ring model”, distinct from the metallogenic model in the NRB, providing valuable guidance for Mn ore prospecting within this area and elsewhere with similar settings.

COMPOSITIONAL AND WEATHERABILITY INDICES OF GETSO KAOLIN DEPOSITS FOR POZZOLANA PRODUCTION

Kaolin is an aluminio-silicate mineral naturally distributed within the earth’s crust formed from the weathering of rich feldspartic rocks. The compositional requirements of Getso kaolin deposits for pozzolana production have been carried out. The kaolin deposits were hosted by the rhyolitic rocks of the basement complex of North-Western Nigeria. Three samples from each five locations at different depths were collected and analysed using Free Swelling Ratio (FSR), Free Swelling Index (FSI), X-Ray Fluorescence Spectrometry (XRF) and Scanning Electron Microscopy/Electron Dispersive X-Ray spectroscopy (SEM/EDS). The FSI and FSR ranged between 0-6-0.9 and 16-36 revealing non-swelling and non-expansive Kaolinitic material. The XRF results showed the average concentration of SiO2+ Al2O3+Fe2O3: point 1 (78.99 wt.%); point 2 (78.62 wt.%); point 3 (79.14 wt.%); point 4 (80.10 wt.%) and point 5 (80.0 wt.%) suggested to be classified as N pozzolana (ASTMC 618). The Fe2O3/MgO versus SiO3 indicated the samples were products of the calc-alkaline series which is an indication of light colour kaolin deposits. The computed Chemical Index of Alteration (CIA: 91.34), Chemical Index of Weatheribility (CIW: 98.13), Index of compositional variability (CIV: 0.29), Silica Modulus Ratio (SM: 1.77), Lime Silica Ratio (LSR: 0.14) and Aluminum Iron Ratio (AIR: 30.0) indicated very strong weathering intensity high matured, high silica moderate aluminum and less ferrite. The studied kaolin could be utilized for the production of pozzolana after its being beneficiated to remove the TiO2.

Linkage between Granite Weathering and Gully Erosion in Subtropical Region

Granites, widely distributed in the Earth’s crust, undergo pedogenic processes, shaping diverse soil-mantled landscapes influenced by climatic factors in different regions. Investigating the geochemical signatures in granite weathering profiles across varying climatic conditions provides valuable insights into the intricate interplay between weathering and landscape evolution. In this study, the geochemical features, particularly major and rare earth elements, and the weathering degree of granites across temperate to subtropical regions in China were examined. The results indicated significant variations in the geochemical characteristics of granite weathering profiles, both at a pedon and regional scale (p &lt; 0.01). With increasing hydrothermal conditions from north to south, soil pH shifted from neutral to acidic, accompanied by the leaching of major elements (K2O, Na2O, CaO, and MgO) and the enrichment of Al and Fe. The total rare earth elements (∑REEs) ranged from 75 to 352 ppm, and light rare earth elements (LREEs) from 71 to 317 ppm, exhibiting less significant variations across the study area, while heavy rare earth elements (HREEs) showed higher concentrations in the subtropical region (3 to 35 ppm). Plagioclases dominated the weathering process in temperate regions, with K-feldspar progressively increasing and, eventually, dominating from temperate to subtropic regions, resulting in a shift in clay minerals from 2:1-type in the temperate to 1:1-type in the subtropic. The chemical index of alteration (CIA) and comprehensive weathering index (W) increased from fresh rock to residual soils along the weathering profiles and from north to south across the study area, ranging from 50.72 to 97.44 and 35.11 to 70.62, respectively. The intensified granite weathering degree was significantly influenced by climatic conditions (p &lt; 0.05), especially the multi-year average precipitation (22.4%) and relative humidity (9.1%) (p &lt; 0.01). Gully erosion on the granite weathering mantle was concentrated in granites with a comprehensive weathering index exceeding 52.51, and the spatial variation of the granite weathering degree aligned with the spatial distribution of gully density across the study area.

Provenance, chemical weathering, and sedimentary environment of the aquifer sediments: Implication for arsenic enrichment in groundwater

High arsenic (As) groundwater has been widely observed in the world, but the provenance, chemical weathering, and sedimentary environment of aquifer sediments hosting high As groundwater remain poorly understood. The geochemical and isotopic characteristics of high-resolution aquifer sediments were investigated to unravel the roles of provenance, chemical weathering, and sedimentary environment of the aquifer sediments. The average values of rare earth elements (REEs) showed the enrichment of light REEs and flat heavy REEs in the aquifer and the Yellow River sediments. The chemical index of alteration reflected incipient and moderate weathering (41 to 71). The δ13CSOM (−27.4‰ ± 4.3‰) and C/N values (8.1 ± 5.8) indicated aquatic environment of sedimentation. Shallow aquifer sediments mostly had relatively high ΣREEs contents and negative Eu anomalies, demonstrating that the aquifer sediments were mainly derived from the Yellow River (up to 94.3% ± 5%). Deep aquifer sediments had relatively low ΣREEs contents and positive Eu anomalies, which originated from the Yinshan Mountains (up to 72.2% ± 20.4%) principally with igneous and metamorphic rocks. Moreover, recycling of the Yellow River sediments from Northeastern Tibetan Plateau enhanced the silicate weathering and increased contents of Fe/Mn oxides and As. The δ13CSOM and C/N values evidenced that organisms of paleo-lake or paleo-Yellow River were responsible for abundant sedimentary organic matter. Concentrations of Fe, Mn, and As were high in shallow groundwater from the plain. The As enrichment in the shallow groundwater was jointly controlled by the provenance and chemical weathering of the aquifer sediments (14%), sedimentary environment (10%), reductive dissolution (35%) of Fe/Mn oxides, As desorption under elevated pH (20%), and competitive adsorption of HCO3- (21%). This study systematically reveals the roles of provenance, chemical weathering, and sedimentary environment of the aquifer sediments and highlights joint contributions of geochemical processes and geochemical conditions to As enrichment in groundwater.

Geochemistry and Provenance of Loess on the Miaodao Islands, China

Loess deposits are widely distributed across the globe and provide detailed records of climatic changes since the Quaternary period. Their geochemical element characteristics are important indicators of paleoenvironmental evolution and provenance. Therefore, four typical loess sections from four different islands of the Miaodao Islands were selected for systematically geochemical analysis of major and trace elements. The geochemical data of major and trace elements are very similar, indicating that the loess of all islands on the Miaodao have a common provenance. The geochemical test results show that t SiO2, Al2O3, Fe2O3 and CaO are the major chemical components of loess, with an average total content of 85–90%. The average Eu/Eu*, ΣLREE/ΣHREE, LaN/YbN, GdN/YbN values of the Miaodao Islands loess range from 0.65 to 0.69, 7.84 to 8.31, 8.02 to 9.99, 1.40 to 1.76. These data are similar to and different from those of the Chinese Loess Plateau, indicating the diversity of Miaodao Islands Loess provenance. The CIA (Chemical Index of Alteration) (50–65) and Na/K results suggest that the loess here had experienced incipient chemical weathering. The A-CN-K (Al2O3-CaO* + Na2O-K2O) diagram indicates that the weathering trend of the loess sections is consistent with that of continental weathering. The local loess data points are close and parallel to the A-CN line, suggesting that the loess dust material on the Miaodao Islands originated from the extensive upper continental crust, and was highly mixed in the process of wind transport and deposition. The relationships of Log[(CaO + Na2O)/K2O] versus Log(SiO2/Al2O3), Na2O/Al2O3 versus K2O/Al2O3, LaN/YbN versus Eu/Eu*, Sc-Th-La and Zr-Sc-Th plots of major and trace elements reveal that the loess sources for the Miaodao Islands are similar to those of the Loess Plateau, which were derived from alluvial fan deposits flanking the Qilian Shan in China, the Gobi Altay and Hangayn Mountains in Mongolia. However, the loess of the Miaodao Islands is coarser in average grain size and contains abundant marine fossils, with gravel layers, indicating it is allochthous and near-source, which suggests it mainly originated from the adjacent exposed sea floor sediments of the Bohai Sea during glacial periods. Finally, we conclude that the loess of the Miaodao Islands is the result of a gradual accumulation process, in which the relative amount of distant-source material decreased and the near-source material increased in response to changes in sea level and paleoclimate. Our findings support that the loess of the Miaodao Islands was formed by mixing material from distant and proximal sources.

Geochemical Record of Late Quaternary Paleodepositional Environment from Lacustrine Sediments of Soda Lake, Carrizo Plain, California

This study investigates the responses of the depositional environments of Soda Lake sediments to climatic shifts from the Last Glacial Maximum to the Holocene epoch based on the results of major and trace elements of the North Soda Lake (NSL) NSL1A core. The NSL1A core records the sedimentary evolution of the Soda Lake watershed since at least 25 cal ka BP. Element analyses provide evidence that Soda Lake sediments are mostly derived from marine sequences in the Southern Coast Ranges of California. Variation in proxies for paleoweathering, paleoclimate, paleosalinity, paleoproductivity, paleoredox, and water depth is utilized to reconstruct the evolution of the sedimentary environment. The Chemical Index of Alteration (CIA) values indicate low to moderate chemical weathering in the sediment source regions. Paleoredox proxies indicate that the NSL1A core formed in a mainly subreduction environment. The NSL1A core is divided into four zones based on the results of the proxies. Zone 4 (5.0–5.8 m) of the sediment core indicates stable hydroclimatic conditions with low and constant sand and silt content, suggesting a warm and relatively humid environment. Zone 3 (3.35–5.0 m) represents the early half of the Last Glacial Maximum interval and a high lake stand. The elevated sand content suggests postflood events due to the northerly migration of westerly storm tracks. Zone 2 (1.075–3.35 m) reveals nuanced changes, including decreasing salinity, slight increases in wetness, detrital trace metals, and paleoproductivity. These subtle shifts suggest a multifaceted environmental evolution: a trend toward wetter conditions alongside a prolonged shift from cooler to warmer periods. Zone 1 (0.15–1.075 m) spans the Lateglacial to Holocene transition as well as Early and Middle Holocene, marked by significant hydrologic and ecologic variability including rapid warming during the Bølling–Allerød and rapid cooling linked to the Younger Dryas.

Geochemistry and petrology of Early Permian lacustrine shales in the Lodève Basin, Southern France: Depositional history, organic matter accumulation and thermal maturity

The lacustrine shales in the Lodève Basin, southern France, serve as excellent archives of paleo-lake development as well as climatic evolution during the Early Permian. In this study, an extensive dataset is presented encompassing organic petrographic data, major and trace element quantification, bulk and molecular organic geochemical proxies, as well as compound-specific stable carbon isotope data derived from the analysis of 36 black shale outcrop samples originating from the Usclas-St. Privat Formation (USPF), Tuilières-Loiras Formation (TLF), and Viala Formation (VF). All sample are thermally oil-mature, as evident from a vitrinite reflectance (VRr) of around 0.8%. The lower section of the USPF, characterized by notably higher total sulfur (TS) concentrations, displays total organic carbon (TOC) and TS contents spanning from 2.69 to 7.83 (avg. 4.28) wt% and 0.42–1.55 (avg. 1.09) wt%, respectively. In contrast, the upper section of the USPF (average TOC of 2.59 wt%), TLF (average TOC of 2.66 wt%), and VF (average TOC of 3.17 wt%) exhibit considerably lower TS contents of 0.26 wt%, 0.22 wt%, and 0.17 wt%, respectively. The lower section of the USPF, characterized by the lowest pristane/phytane (Pr/Ph) ratio and the highest TS/TOC ratios and chemical index of alteration (CIA) values, was deposited in oxygen-depleted and saline lacustrine environments. These conditions prevailed under more humid climatic conditions and were probably related to marine incursions. In contrast, the upper section of the USPF, the TLF, and the VF display elevated Pr/Ph ratios but reduced TS/TOC and CIA values, signifying deposition within oxic-dysoxic and freshwater-brackish bottom water conditions with a significant change towards arid conditions. All samples are characterized by low vitrinite and inertinite contents together with consistently similar average values of Al2O3 and TiO2. The biomarker analysis suggests that the organic matter (OM) in most samples mainly originates from planktonic/algal biomass with additional microbial OM. Only the lower section of the USPF displays a slightly enhanced contribution of terrestrial OM input and also more detrital elements. It is concluded that the structural evolution of the basin from narrow deep towards wider and shallower settings as well as the postulated marine transgressive events during early stages played a crucial role in shaping the deposition environments of the two distinct sets of lacustrine shales, thereby influencing the OM accumulation mechanisms. In contrast, the substantial climatic aridification seems to have a relatively minor impact on the sources of OM and the conditions prevailing within the water column.

Millennial-scale variability of Greenland dust provenance during the last glacial maximum as determined by single particle analysis

Greenland ice core records exhibited 100-fold higher dust concentrations during the Last Glacial Maximum (LGM) than during the Holocene, and dust input temporal variability corresponded to different climate states in the LGM. While East Asian deserts, the Sahara, and European loess have been suggested as the potential source areas (PSAs) for Greenland LGM dust, millennial-scale variability in their relative contributions within the LGM remains poorly constrained. Here, we present the morphological, mineralogical, and geochemical characteristics of insoluble microparticles to constrain the provenance of dust in Greenland NEEM ice core samples covering cold Greenland Stadials (GS)-2.1a to GS-3 (~ 14.7 to 27.1 kyr ago) in the LGM. The analysis was conducted on individual particles in microdroplet samples by scanning electron microscopy with energy dispersive X-ray spectroscopy and Raman microspectroscopy. We found that the kaolinite-to-chlorite (K/C) ratios and chemical index of alteration (CIA) values were substantially higher (K/C: 1.4 ± 0.7, CIA: 74.7 ± 2.9) during GS-2.1a to 2.1c than during GS-3 (K/C: 0.5 ± 0.1, CIA: 65.8 ± 2.8). Our records revealed a significant increase in Saharan dust contributions from GS-2.1a to GS-2.1c and that the Gobi Desert and/or European loess were potential source(s) during GS-3. This conclusion is further supported by distinctly different carbon contents in particles corresponding to GS-2.1 and GS-3. These results are consistent with previous estimates of proportional dust source contributions obtained using a mixing model based on Pb and Sr isotopic compositions in NEEM LGM ice and indicate millennial-scale changes in Greenland dust provenance that are probably linked to large-scale atmospheric circulation variabilities during the LGM.

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.

Petrography, geochemistry and detrital zircon U–Pb dating of the Pliocene‐Pleistocene Dupi Tila Formation from the Lalmai Anticline, Bengal Basin: Regional tectonic implications

The Bengal Basin is a well‐known foreland basin that archives the tectonic evolution of the Himalayan and Indo‐Burman Ranges (IBR). The Dupi Tila Formation is the youngest among the stratigraphic successions of the Bengal Basin, which witnessed the last phase of the Himalayan uplift. However, there is still controversy regarding sediment provenances since the Himalayan and IBR are in the late Neogene exhumation stage. In this study, the petrographical and geochemical compositions of the Dupi Tila sandstones from the Lalmai Anticline of the Bengal Basin are examined to infer the source rocks, tectonic settings, palaeoclimate and weathering intensity in provenance areas. The detrital modes and geochemical discriminations, as well as Chondrite‐normalized rare earth elements patterns with enrichment in light rare earth elements and nearly flat heavy rare earth elements and negative Eu anomalies (average Eu/Eu* = 0.77) indicate dominantly felsic source rocks. The geochemical data also suggest that these source rocks in provenance areas were influenced by weak to moderate chemical weathering (chemical index of alteration: 65.64–75.62) and multiple recycling under warm and humid to semi‐humid climatic conditions. The detrital zircon ages show three dominant peaks at ca. 100, 500 and 1000 Ma with minor 1700 Ma. The amount of young zircon grains (&lt;120 Ma) is noticeably higher (~18%) in this Lalmai outcrop compared to the Dupi Tila samples from the Sylhet Trough and Chittagong‐Tripura Fold Belt. Results from integrated zircon geochronology and geochemistry indicate that the detritus are likely derived from a recycled orogen provenance related mainly to active continental margin setting with subordinate influence from passive setting. Therefore, the regionally extensive Himalayan Orogen appears to be the primary sediment source, with additional mixing from the IBR and recycled sediments originating from the Gangdese batholith of the Trans‐Himalaya.

Tungsten stable isotope composition of the upper continental crust

Tungsten (W) stable isotope data for twenty-four composites made from the fine-grained matrix of glacial diamictites, deposited between the Mesoarchean and the Paleozoic, as well as two Archean tonalite-trondhjemite-granodiorites (TTG) are used to refine the W isotope compositions (expressed as δ186W deviations from the NIST 3163 W standard) of the upper continental crust (UCC). To do this we evaluate W isotope fractionation in the diamictites as the result of both magmatic and low-temperature processes. The δ186W values of the diamictites are heterogeneous (0.017 ± 0.011 ‰, 2SE to 0.182 ± 0.007 ‰, 2SE), encompassing the range of previously published values for igneous rocks. We find that δ186W correlates positively with the diamictite’s chemical index of alteration (CIA), a measure of the degree of chemical weathering in the provenance, suggesting that the continental regolith (i.e., surface material composed of weathered residues) is isotopically heavy for W. Since W in rivers and ocean water is also isotopically heavy, this suggests that equilibration with Fe-Mn-oxides controls the W isotope composition of surface waters and that such oxides are not important constituents of the regolith, whose W is likely accommodated in clays. Using diamictites with low CIA (<60, n = 9), we calculate an average δ186W of 0.046 ± 0.036 ‰ (2SD) for the UCC, from 2.3 to 0.3 Ga. This average is combined with the TTG data of this study, as well as data from the literature for upper crustal rocks to obtain a representative δ186W value of the UCC of 0.046 ± 0.046 ‰ (2SD). The W stable isotope composition of the UCC is lighter than that of mantle-derived melts (MORB and OIB, with an average δ186W = 0.082 ± 0.026 ‰, 2SD), and much lighter than the weighted average δ186W of intra-oceanic arcs (δ186W = 0.104 ± 0.052 ‰, 2SD), though the spread in the arc rocks is large. The significant difference in δ186W between average intra-oceanic island arc lavas and UCC is intriguing given that continental crust is thought to form primarily via arc magmatism. This difference suggests that not all modern intra-oceanic arcs are representative of those that formed the continental crust. Rather, only arcs that are enriched in incompatible trace elements, which also tend to have lighter W isotope compositions, may have been involved in making new continental crust. Alternatively, there may have been a secular change in the W isotope composition of arc magmas.

Geochemical and mineralogical proxies from the Messinian mudrocks (Catanzaro Basin, southern Italy): Paleoweathering and paleoclimate evolution during the onset of the Messinian salinity Crisis

The bulk mineralogy and geochemistry of mudrock samples from a representative section of the Calcare di Base Formation outcropping in the Catanzaro Basin (Calabria) were studied using X-Ray Diffraction and X-Ray Fluorescence techniques. Phyllosilicates are the main mineralogical constituents followed by quartz, calcite, feldspar, hematite and gypsum in the lower part of the studied succession, whereas calcite is the main mineralogical component in the upper part. The geochemical composition reveals that SiO2, Fe2O3, Al2O3, CaO and MgO are the most abundant oxides on average. The chemical weathering indices, such as the CIA (Chemical Index of Alteration) and its modifications, show low-medium values and thus suggest weak-moderate source area(s) weathering conditions, under a mainly dry/arid paleoclimate environment. The low kaolinite amounts confirm a low-moderate degree of weathering processes. The studied samples originate from an environment in which non-steady-state weathering conditions prevailed and active tectonism allows erosional processes. This trend suggests a paleoclimate characterized by persistent dry (arid) conditions alternating with relatively wet (humid) conditions. The studied mudrocks are characterized by recycling effects as recorded in the Al–Zr–Ti plot. The provenance of the studied samples is mainly related to a felsic source such as the rocks composing the Sila Massif.The composition of the studied samples was compared to that of similar samples from the Calcare di Base formation of the Rossano Basin to reconstruct the paleoclimate scenario of the Mediterranean area during the Messinian Salinity Crisis. The analogies between the mudrocks investigated in this work and the argillaceous marls from the Calcare di Base formation of the Rossano Basin suggest that they formed in the same (i) non-steady-state weathering and (ii) dry/arid paleoclimatic conditions. All the evidences allow to hypothesize that semi-closed basins, even if distant and not necessarily synchronous from each other, may have developed in a comparable way due to similar local climate condition, geochemistry of the body water and river run-off. The geochemical and mineralogical proxies from the mudrocks of the Calcare di Base Formation may open a new scenario for the understanding of paleoclimatic condition during the Messinian Salinity Crisis.

The effect of weathering on cohesion in granitic fault rocks: A case study from the Yeongdeok Fault, South Korea

Weathering can alter fault-rock cohesion, which is an important criterion in the classification of fault rocks, and can also alter fault-rock mechanical and hydraulic properties. To investigate the effects of weathering on fault rocks, we studied relatively fresh and weathered fault rocks collected from a drill core and outcrop, respectively, of a granitic fault zone (the Yeongdeok Fault, a northern branch of the Yangsan Fault) on the southeastern Korean Peninsula. At the studied outcrop, the Yeongdeok Fault has juxtaposed Triassic granite against Cretaceous sedimentary rocks. Granitic fault rocks in the outcrop are incohesive, whereas the drill core includes both cohesive and incohesive granitic fault rocks. A detailed correlation of the fault rocks from the drill core with those from the outcrop reveals that some incohesive fault rocks from the outcrop are weathered cataclasite. Cataclasites from the drill core are composed of feldspar, plagioclase, and quartz fragments embedded in a matrix of quartz, plagioclase, muscovite, and chlorite. Locally, foliation defined by the preferred orientation of muscovite is developed. The weathered cataclasite comprises quartz, plagioclase, and feldspar fragments, with a fine-grained matrix composed mostly of clay minerals. The measured Chemical Index of Alteration (CIA) values for cataclasite and weathered cataclasite are 47–49 and 60–67, respectively. Measurements of hydraulic properties show that weathered cataclasite has higher porosity and permeability compared with unweathered cataclasite. Physical and chemical weathering are interpreted to have increased the fracture density of the weathered cataclasite and enhanced the dissolution of vein minerals, respectively. These processes have not only contributed to the higher permeability and porosity of the weathered (cf. unweathered) cataclasite but have also resulted in a loss of cohesion. When cohesion is lost due to weathering, distinguishing between cataclasite and fault breccia becomes challenging. Our study demonstrates that the cohesion-based classification of fault rocks becomes limited for fault rocks with CIA value more than 60.