Search Results (43)

The Sanandaj–Sirjan Zone and Zagros Fold–Thrust Belt in Iran host numerous Mediterranean-type karst bauxite deposits; however, their formation mechanisms and critical raw material potential remain ambiguous. This study combines mineralogical and geochemical analyses to explore (1) the formation of authigenic minerals, (2) the role of microbial organic processes in Fe cycling, and (3) the assessment of their critical raw materials potential. Mineralogical analyses of the Late Cretaceous Daresard and Middle–Late Permian Yakshawa bauxites reveal distinct horizons reflecting their genetic conditions: Yakshawa exhibits a vertical weathering sequence (clay-rich base → ferruginous oolites → nodular massive bauxite → bleached cap), while Daresard shows karst-controlled profiles (breccia → oolitic-pisolitic ore → deferrified boehmite). Authigenic illite forms via isochemical reactions involving kaolinite and K-feldspar dissolution. Scanning electron microscopy evidence demonstrates illite replacing kaolinite with burial depth enhancing crystallinity. Diaspore forms through both gibbsite transformation and direct precipitation from aluminum-rich solutions under surface conditions in reducing microbial karst environments, typically associated with pyrite, anatase, and fluorocarbonates under neutral–weakly alkaline conditions. Redox-controlled Fe-Al fractionation governs bauxite horizon development: (1) microbial sulfate reduction facilitates Fe³⁺ → Fe²⁺ reduction under anoxic conditions, forming Fe-rich horizons, while (2) oxidative weathering (↑Eh, ↓moisture) promotes Al-hydroxide/clay enrichment in upper profiles, evidenced by progressive total organic carbon depletion (0.57 → 0.08%). This biotic–abiotic coupling ultimately generates stratified, high-grade bauxite. Finally, both the Yakshawa and Daresard karst bauxite ores are enriched in critical raw materials. It is worth noting that the overall enrichment appears to be mostly driven by the processes that led to the formation of the ores and not by the chemical features of the parent rocks. Divergent bauxitization pathways and early diagenetic processes—controlled by paleoclimatic fluctuations, redox shifts, and organic matter decay—govern critical raw material distributions, unlike typical Mediterranean-type deposits where parent rock composition dominates critical raw material partitioning. Full article

Palygorskite is assumed to be the predominant clay mineral in playa-lakes, where it may be detrital or authigenic in origin. Discriminating between detrital and authigenic clays is crucial to elucidate paleoenvironmental conditions in lacustrine deposits. This study provides insight into the sedimentary evolution of clay minerals from source, lacustrine Miocene marlstones and mudstones, to sink, represented by three recent hyperalkaline playa-lakes in Central Spain. XRD, TEM, and AEM analyses show concomitant detrital and authigenic palygorskites in the three playa-lakes. The inherited palygorskites exhibit degradation features, larger widths, and common and ideal compositions, in contrast to neoformed particles. The latter are narrower. Depending on the hydrochemical composition of each playa-lake, neoformed palygorskites are enriched in a different octahedral cation (Al₂O₃, MgO, and Fe₂O₃). Iron-rich palygorskites are only formed in association with authigenic saponites in one of the playa-lakes. The same effect of magnesium competition between smectite and palygorskite is observed in Miocene mudstones, where palygorskite is relatively enriched in iron. In hyperalkaline, seasonal playa-lakes lying in the vicinity, slight physicochemical differences play a crucial role in the crystallochemical composition of authigenic palygorskites, highlighting the use of this mineral as a geochemical proxy. Full article

This study aimed to develop a geochemical database by thoroughly analyzing groundwater and sediments from coastal aquifers of southwest Bangladesh. Moreover, we investigated the source of sediment deposition and the mechanisms behind the presence of arsenic and salinity in groundwater. The seasonal distribution patterns of arsenic among the shallow and deep coastal aquifers were found to be 45.12 µg/l and 20.65 µg/l during dry and wet seasons, respectively. Moreover, the groundwater salinity distribution ranged from 3262.88 mg/l to 1930.88 mg/l during the dry and wet seasons. Cored sediment samples showed fine to medium sands of 92%, with silt and clay particles. The petrographic study of authigenic and heavy minerals revealed that the mineral grains were subangular to angular, indicating their textural immaturity of coastal sediments. The reactivity of goethite (FeOOH) and siderite (FeCO₃) minerals suggests that the aquifers were subjected to slightly oxidized to moderately reducing conditions, with ORP values ranging from +50.40 mv to −149.5 mv. Such redox conditions could potentially result in the enrichment and mobility of arsenic in the groundwater. Although arsenic concentrations in deep aquifers are relatively low, higher salinity values are found in both shallow and intermediate coastal aquifers. Full article

The Late Permian coal measures in eastern Yunnan, western Guizhou, and central Guangxi are significantly enriched in critical metals that could serve as important supplements to conventional critical metal deposits in China. This study collected previous geochronological and geochemical data from the Late Permian coal measures to evaluate the distribution characteristics and enrichment factors of critical metals. Moreover, metallogenic models for critical metals were also developed. The results showed that Late Permian coal measures in Yunnan, Guizhou, and Guangxi provinces exhibited abnormal enrichment in Nb, Zr, and rare earth elements (REY, or REE if Y is excluded). The Emeishan mafic rocks and intermediate-felsic volcanic ash from the Truong Son orogenic belt underwent chemical weathering, with Nb and Zr selectively preserved in situ in the form of heavy minerals (e.g., rutile, zircon, and anatase), which subsequently led to the enrichment of Nb and Zr in bauxite and Al-claystone at the bottom of the Late Permian coal measures. Intermediate-felsic volcanic ash from the Emeishan large igneous province (ELIP) and the Truong Son orogenic belt supplied Nb, Zr, and REY for the middle and upper parts of the Late Permian coal measures. The intermediate-felsic mineral material of the coal measures in the intermediate zone, outer zone, and outside zone of ELIP are derived mainly from the ELIP, the mixture from ELIP and the Truong Son orogenic belt, and the Truong Son orogenic belts, respectively. Nb, Zr, and REY were leached by acidic aqueous solutions and from the parting and roof into underlying coal seams, where they deposited as authigenic minerals or adsorbed ions on organic matter during early coalification. Full article

Deep-sea sediments enriched in rare earth elements and yttrium (REY-rich sediments) are widely distributed on the deep-sea floor, and their formation mechanism remains elusive. Although studies have recognized the link between seamounts and REY-rich sediments, in-depth analysis of the specific roles and effects of seamounts in the formation of REY-rich sediments is lacking. In this study, we analyzed surface sediments from the Marcus-Wake Seamounts for grain size, geochemistry, and mineral composition and classified the samples into three types: samples with moderate REY content and dominated by terrestrial detritus; samples with high REY and authigenic mineral content; and samples rich in CaCO₃ but poor in REY. The REY in the sediments of the study area partly originate from Asian dust input and partly from seawater and/or pore water, and are mainly enriched in REY carrier particles including bioapatite fossils and micronodules. The amount of REY carrier particles influences the REY content in the sediments. The current field, primary productivity, weathering process, and depositional environment around seamounts are different from those of abyssal plains, which are conducive to the formation of REY-rich sediments. Strong bottom currents may exist in the southeastern direction of some large seamounts (e.g., Niulang Guyot), leading to the selective accumulation of REY-rich bioapatite fossils and micronodules, resulting in the formation of REY-rich sediments. Full article

An in situ electron microprobe study of detrital minerals yielded important insights into the diagenetic history of the Cretaceous-to-Paleogene flysch sandstones from the Chvalčov site, Rača Unit, Flysch Belt of the Outer Western Carpathians. Detrital titanite and a Fe-Ti mineral (probably ilmenite) were almost completely altered to TiO₂ minerals, which also newly crystallized in intergranular spaces of sandstone. Brookite, anatase, and, exceptionally, rutile were identified by Raman spectroscopy. Authigenic TiO₂ phases show complex composition with occasionally elevated contents of Fe, Nb, Zr, V, Sc, Cr, Al, Y, and/or P, which were likely sourced from altered neighboring heavy minerals. In addition, rare authigenic LREE- and Y-enriched apatite rims were observed on detrital apatite. The remobilization of REE, Y, and HFSE was likely mediated by acidic early diagenetic fluids enriched in fluoride and sulfate anions. The superimposed formation of calcite cement was associated with the dissolution of detrital garnet, feldspars, and quartz. The compositions of detrital apatite and garnet (Alm_60-82Prp_4-30Sps_0-24Grs_0-19) are comparable with those from adjacent parts of the Flysch Belt. Detrital rutile is enriched in Nb, V, Cr, and Zr. Our study illustrates the intensity of diagenetic alteration of detrital minerals in flysch sandstones as well as the usefulness of in-situ electron-microprobe investigations for the recognition of processes influencing heavy minerals in diagenetically altered sediments. Full article

Time-series samples intercepted via three synchronized moored sediment traps, deployed at 1000 m, 2150 m, and 3200 m in the northern South China Sea (NSCS) during June 2009–May 2010, were analyzed to quantify the bioactive trace metal fluxes in sinking particles and investigate their different source contributions. Iron (Fe) primarily originated from lithogenic sources. Manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) exhibited various degrees of enrichment over their continental crustal ratios. Since the sources of bioactive trace metals in sinking particles can be divided into lithogenic, biogenic, and excess fractions, mass conservation calculations were used to quantify the contribution of each source. The results showed that Fe, Mn, and Co had extremely low biogenic proportions (0.1–3.3%), while Ni, Cu, and Zn had higher proportions (2.7–17.3%), with the biogenic fraction decreasing with the depth. Moreover, excess sources accounted for a significant proportion of Mn (68–75%), Co (34–54%), Ni (60–62%), Cu (59–74%), and Zn (56–65%) in sinking particles at the three sampling depths. The excess fractions of Mn, Co, and Cu in sinking particles can be affected by authigenic particles. This is supported by their similar scavenging-type behavior, as observed via the increase in their fluxes and enrichment patterns with the increasing depth. Furthermore, the excess fractions of Ni, Cu, and Zn may have significant contributions from anthropogenic sources. The variability of Fe in sinking particles was mainly controlled via lithogenic matter. Notably, organic matter and opal were found to be pivotal carriers in the export of excess bioactive trace metals (Mn, Co, Ni, and Cu) via the water column, accompanied with the elevated ballast effect of lithogenic matter with the depth. However, the transportation of excess Zn was more complicated due to the intricate processes involved in Zn dynamics. These findings contribute to our understanding of the sources and transport mechanisms of bioactive trace metals in the marine environment. Full article

Towards a better understanding of factors controlling carbon (C) exchange between inland waters and atmosphere, we addressed the inorganic carbon cycle in semiarid lakes of Central Eurasia, subjected to the strong impact of on-going climate change. As such, we assessed the hydrochemical variability and quantified its control on the formation of authigenic carbonate minerals, occurring within the upper layer of sediments in 43 semiarid lakes located in the southwest of Western Siberia (Central Eurasia). Based on measurements of pH, total dissolved solids (TDS), cationic and anionic composition, dissolved organic and inorganic C, as well as textural and mineralogical characterization of bottom sediments using X-ray diffraction and scanning electron microscopy, we demonstrate that lake water pH and TDS are primarily controlled by both the lithological and climatic context of the lake watershed. We have not revealed any direct relationships between lake morphology and water chemistry. The most common authigenic carbonates scavenging atmospheric CO₂ in the form of insoluble minerals in lake sediments were calcite, aragonite, Mg-calcite, dolomite and hydromagnesite. The calcite was the most common component, aragonite mainly appears in lakes with sediments enriched in gastropod shells or artemia cysts, while hydromagnesite was most common in lakes with high Mg/Ca molar ratios, as well as at high DIC concentrations. The relationships between mineral formation and water chemistry established in this study can be generalized to a wide suite of arid and semiarid lakes in order to characterize the current status of the inorganic C cycle and predict its possible modification under on-going climate warming such as a rise water temperature and a change in hydrological connectivity, primary productivity and nutrient regime. Full article

Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling. Full article

The sedimentary basin of Podillya (Volyno-Podillya-Moldavia) is situated in the southwest of the Ukrainian crystalline shield and belongs to the middle part of the Upper Neoproterozoic section of the Moguiliv-Podilska Group. By analyzing the primary oxide, trace, and rare-earth element compositions of the phosphate nodules in the area, this study sought to shed light on the potential precipitation characteristics of the Ediacaran Sea, where phosphate nodules were created. The mean major oxide contents of the nodules were 50.8 wt.% CaO, 34.2 wt.% P₂O_5, 5.29 wt.% SiO₂, 4.77 wt.% LOI, 1.69 wt% Fe₂O₃, 1.63 wt% Al₂O₃, and 0.35 wt.% MnO. The average trace element concentrations were 183 ppm Ba, 395 ppm Sr, 13.4 ppm Ni, 32.7 ppm Cr, 62.2 ppm Zn, 764 ppm Y, 16 ppm V, 10.8 ppm As, 75.8 ppm Cu, 84 ppm Pb, 2.1 ppm U, 1.7 ppm Th, and 4.2 ppm Co. The trace element contents were generally low and indicated an assemblage of Cu, Y, As, Cd, and Pb enrichments in comparison to PAAS. The total REE concentrations varied from 1638 ppm to 3602 ppm. The nodules had medium REE (MREE) enrichments and showed similar REE patterns normalized to PAAS. All the nodules had strongly negative Ce, Pr, and Y anomalies and substantially negative Eu anomalies, with four samples being exceptions. These abnormalities suggest that oxic and suboxic sea conditions existed at the time the nodules formed. The extremely high REE concentrations are thought to be the result of REEs being redistributed between the authigenic and detrital phases that were created during the diagenetic equilibration of phosphate with pore water. The genetic hypothesis for phosphate nodule formation states that the nodules were generally formed in oxic and suboxic seawater and were precipitated on slopes in response to a significant upwelling from a deeper basin with abundant organic matter under anoxic/suboxic conditions. The majority of the organic material at the water–sediment interface of the seafloor underwent oxidation before phosphate was released into the pore water of the sediment. Full article

Syndepositional diagenesis is a complicating factor when interpreting geochemical proxies in carbonate sedimentary environments. Previous studies have suggested that carbonate deposits may preserve the geochemical and isotopic signatures of seawater that can be used for paleo-redox reconstructions. However, more work is necessary to understand how these trace metals are preserved. The present study examines shallow marine carbonate sediments from the Bahamas to better understand diagenetic effects on trace metal uptake and sequestration. Analysis of diagenetic effects and trace metal uptake follows a multi-method approach, combining sequential extraction, stable isotope analyses, and rare earth elemental analysis. Stable isotopes track bacterial sulfate reduction, denitrification, and organic matter source and provide insight into thresholds and processes for the authigenic trace metal uptake. Importantly, exchangeable phases exhibit authigenic accumulation of molybdenum, uranium and vanadium, and intensified bacterial sulfate reduction is evidenced by most depleted sulfur isotope signatures. In addition, rare earth element values are very indicative proxies that suggest altered primary seawater trace element in carbonates (no cerium or lanthanum anomaly, moderate heavy rare earth element enrichment, decreased y/ho ratios and positive correlations between aluminum, manganese, and iron). Taken together, these results allow the development of a framework to better understand how to apply sedimentary geochemistry of carbonate rocks to paleo-environments as this study shows significant authigenic accumulation of redox-sensitive trace metals by exchangeable phases. Full article

Lake sediments accumulate various pollutants and act as efficient natural archives suitable for reconstruction the environmental conditions of the past. In contrast to fairly good knowledge of mineral sediments in lakes of European and North America boreal lakes, Siberian lakes of the boreal zone remain quite poorly studied. In this work, two cores of lake sediments of the Ob River valley were investigated. Elemental analyses were carried out on the sediments, losses on ignition were determined, and the rate of sedimentation was measured from the activity of Pb-210 and Cs-137. According to the content of organic matter, bottom sediments belong to different types: clastic (Lake Inkino, located in the Ob River floodplain) and organogenic (Lake Shchuchie on the second terrace). The rate of sedimentation in Lake Shchuchie is several times higher than that in Lake Inkino. The sediments of Lake Inkino are similar in composition (including the pattern of rare earth elements) to the suspended particulate matter of the Ob River as well as to average detrital matter of the upper continental crust. Sediments of Lake Shchuchie (sapropels) are enriched in a number of heavy metals. Based on the elemental composition, signs of diagenetic processes and authigenic mineral formation were determined, such as accumulation of carbonates and the formation of manganese oxides and hydroxides. There is an enhanced recent input of Cr, Co, Cu, Zn, Cd, Sb, Pb, and Bi in the upper layers of sediments as a result of atmospheric anthropogenic pollutant deposition. Full article

The role of biogenicity in the mineral world is larger than many might assume. Biological processes and physical and chemical processes interact both at the Earth’s surface and far underground, leading to the formation of banded iron and manganese deposits, among others. Microbial mats can form giant sedimentary ore deposits, which include enrichment of further elements. This article reviews the ways in which microbially-mediated processes contribute to mineralization, the importance of mineralized microbial textural features, and the methods that must be used to obtain high-resolution datasets. If the chosen methodology and/or the size dimension of investigation is not appropriate, then it is not possible to recognize that a system is microbially mediated, and the conclusion will be incomplete. We call attention to variable authigenic mineralization as the result of complex mineralization of cells and extracellular polymeric substances in the starving basins, which form giant ore deposits together with ore-forming minerals. Microbial mats and other biosignatures can serve as indicators of environmental reconstruction in ore formations. We suggest tests and analyses that will allow the potential role of biomineralization to be properly investigated for a more comprehensive view of formation processes and their implications. Full article

The geochemistry and mineralogy of sediments provide relevant information for the understanding of the origin and metallogenic mechanism of ferromanganese nodules and crusts. At present, there are still few studies on the sediment origin of the Clarion–Clipperton Zone (CCZ) of the east Pacific, particularly on the systematic origin of sediments with a longer history/length. Here, bulk sediment geochemistry and clay mineral compositions were analyzed on a 5.7 m gravity core (GC04) obtained at the CCZ, an area rich in polymetallic nodules. The results indicate that the average total content of rare earth elements (REE), including yttrium (REY), in sediments is 454.7 ppm and the REEs distribution patterns normalized by the North American Shale Composite of samples are highly consistent, with all showing negative Ce anomalies and more obvious enrichment in heavy REE (HREE) than that of light REE (LREE). Montmorillonite/illite ratio, discriminant functions and smear slide identification indicate multiple origins for the material, and are strongly influenced by contributions from marine biomass, while terrestrial materials, seamount basalts and their alteration products and authigenic source also make certain contributions. The REY characteristics of the sediments in the study area are different from those of marginal oceanic and back-arc basins, and more similar to pelagic deep-sea sediments. Based on LREE/HREE-1/δCe and LREE/HREE-Y/Ho diagrams, we conclude that samples from the study area had pelagic sedimentary properties which suffered from a strong “seawater effect”. Full article

Effective shale gas exploration is hindered by the need for obtaining high-resolution correlations between shale strata and the need for classifying shale facies. To address these issues, chemostratigraphy, sequence stratigraphy, and shale gas geology methods were integrated to develop a new method known as “chemical sequence stratigraphy,” which was successfully applied to the Wufeng–Lower Longmaxi Formations in the upper Yangtze region. Well Huadi 1 was used as a case study, and detailed data were acquired. Multivariate statistical analyses were applied to three defined indices having different genetic significance, namely: terrigenous input intensity (TII), authigenic precipitation intensity (API), and organic matter adsorption and reduction intensity (OARI). By analyzing the trends of these three indices, the Wufeng–Lower Longmaxi Formations were divided into five fourth-order chemical sequences (from bottom to top): LCW, MCL1-1, MCL1-2, MCL1-3, and MCL1-4. The geochemical facies were named and classified using the chemical sequence stratigraphic framework. The enrichment factor (EF) transformation of elements was conducted to determine whether an element is rich or deficient. The results showed that the favorable geochemical facies in the well were EF-Al deficient, EF-Ca rich, and EF-V rich. The organic matter content and rock brittle strength were then used as chemical parameters, and it was predicted that the LCW and MCL1-1 chemical sequences most likely comprised shale gas sweet spots. This conclusion is consistent with the drilling results and indicates that our proposed method is effective and reliable. This method is further applied to the Changning Shuanghe section, the Shizhu Liutang section, and sections in the Xindi 1 well in the upper Yangtze region. The comparative study of these four sections showed that LCW and MCL1-1 are the key chemical sequences for shale gas exploration and development in the Wufeng–Lower Longmaxi Formations within the Upper Yangtze region. Full article