Rare Earth Elements And Yttrium Research Articles

The rare earth elements and yttrium (REY) geochemistry of the upper Carnian (Upper Triassic) carbonates from northwestern Sichuan Basin (South China)

Rare earth elements and yttrium (REY) serve as valuable tracers of the geochemical properties of paleo-seawater and diagenetic processes. Four different carbonate components, ooids, microbalites, cements and brachiopods, from upper Carnian (Upper Triassic) of the northwestern Sichuan Basin were analyzed for REY geochemistry. Petrographic and cathodoluminescence analyses were employed to identify diagenetic features. The bright luminescent microspar calcite cement, ooids and the microbialites from the lower part of Qingyangou (HWQ) section exhibit bell-shaped REYSN patterns. Microbialites from the upper part of HWQ section have relatively high REY concentrations with a flat REYSN pattern. The high content of ΣREY and terrigenous elements (e.g., Al, Zr, Th) in ooids and microbialites reflect the input of terrigenous clastic in the northwestern Sichuan Basin during Late Carnian. Articulated terebratulid brachiopods in the study area display a generally modern seawater-like REYSN pattern. However, this pattern may be influenced by the presence of sparry cement that has infilled the cracks and punctae of the brachiopod shells. The ooids, microbalites, cements and brachiopods are unsuitable for reconstructing the REY characteristics of Carnian seawater in the northwestern Sichuan Basin due to diagenetic alteration and terrigenous input. This study also highlights the necessity of thoroughly evaluating carbonate components for diagenetic effects and terrigenous contamination when employing them for REY characteristic reconstruction.

Interplay and feedback between tectonic regime, faulting, sealing horizons, and fluid flow in a hydrocarbon-hosting extensional basin: The Val d'Agri Basin case, Southern Italy

Understanding the factors that govern past fluid circulation in tectonically active and/or hydrocarbon-rich basins is crucial for elucidating present-day fluid-flow scenarios. We investigate the circulation of paleo-fluids in the extensional-transtensional Val d'Agri Basin (southern Italy), home to a giant oil field and significantly affected by both natural and human-induced seismicity. Our aim is to understand how faulting and the variable thickness of the clay-rich tectonic mélange, which constitutes the seal of the hydrocarbon reservoir, influenced past fluid flow under different tectonic regimes. To achieve this, we combined multiscale structural observations with isotope (C, O, clumped, and Sr) and Rare Earth and Yttrium (REY) analyses of fault-related calcite mineralizations. Using analytical methodologies that allow the analysis of sub-milligram samples for carbonate clumped isotopes, we provided a detailed characterization of the variability in precipitation temperatures and composition of parental fluids in both space and time. Our results reveal five main types of parental fluids, ranging from meteoric to intraformational and deep crustal, which were differently involved in the tectonic evolution of the Val d'Agri Basin. During orogenic shortening, vertical fluid circulation was mostly limited and compartmentalized, whereas post-orogenic extensional faulting promoted the ascent of deep fluids. Our findings indicate that the sealing properties of the mélange were likely enhanced locally by increased thickness but were also compromised by fault activity and associated seismic events. Fluid circulation in the study area has been influenced by the prevailing tectonic regime (compressive vs. extensional), stratigraphic-structural architecture, properties of impermeable horizons, and seismic events. The model proposed for the Val d'Agri Basin elucidates past processes that are useful for understanding current fluid circulation in the basin itself and can be applied to other basins where fluid circulation is partly manipulated by human activities.

Assessment of REY resource potential in deep-sea sediments with Fe–Mn (oxyhydr)oxides in the Pacific Ocean

Deep-sea sediments with an abundance bioapatites and Fe–Mn (oxyhydr)oxides in the Pacific Ocean have been considered potential reservoirs of rare earth elements and yttrium (REY). However, comprehensive assessment of the resource potential of REY in deep-sea sediments with Fe–Mn (oxyhydr)oxides throughout the Pacific Ocean is limited due to difficulties in accurately predicting the distribution of extensive Fe–Mn (oxyhydr)oxides and the associated REY. In this study, we predicted the prospective area and resource potential of REY-rich sediments with Fe–Mn (oxyhydr)oxides by considering multiple factors that control REY enrichment based on data from International Ocean Discovery Program (IODP) samples and previous research. According to the distribution map inferred by comprehensively evaluating lithology (clay sediment), hydrothermal fluid influence (δ3He), and water depth (bathymetry), deep-sea sediments with Fe–Mn (oxyhydr)oxides, which have higher than 1000 ppm REY concentration, are distributed in the vicinity of the East Pacific Ridge within a water depth range of 4000–4600 m, and their distribution area is estimated to be approximately 1.1 million km2. If the sedimentation rate (<1.5 m/Myr) is considered, which is a crucial factor influencing REY enrichment, we can achieve a more precise assessment of their distribution area. Assuming a recovery depth of only 1 m, the REY resource amount was estimated to be approximately >450 million tons of REY oxide. Even without accounting for REY resource amount associated with bioapatite, the minimum REY resource amount estimated in this study exceed the world's current land reserves. Furthermore, these sediments contain a significant abundance of industrially important heavy REY, accounting for 53 % of REY resources. This implies that the deep-sea sediments with Fe–Mn (oxyhydr)oxides in the Pacific Ocean are a promising resource of REY. Our findings will serve as essential information for the technological progress required in the exploration and development of REY resources in deep-sea sediments in the future.

Enhanced deep-water circulation facilitated rare earth elements enrichment in pelagic sediments from the northwestern Pacific Ocean

The lack of knowledge about the enrichment mechanism of rare earth elements and yttrium (REY) in deep-sea sediments is impeding the development of theories and exploration strategies for pelagic REY-rich sediments. Ocean circulation variability seems to be crucial in enriching REY in pelagic sediments, which, however, has not been extensively studied. Here, we examined the Pb-Nd isotopic signals of bottom water recorded by the authigenic ferromanganese oxyhydroxide fractions, as well as the Mn/Al and Mn/Ti ratios of bulk samples from a well-dated sediment core in the northwestern Pacific Ocean. These proxies consistently indicate that enhanced deep-water circulation occurred in the study area at ∼11.5–9.5 Ma, which was most likely to be caused by changes in the flow path of bottom currents. The age of this distinct event consists with the forming age of highly REY-rich sediments. We propose that enhanced deep-water circulation in seamount areas could increase the flux of micronodules and fish debris into the pelagic sediments, facilitating the scavenging of REY from seawater. Our findings establish a connection between enhanced deep-water circulation and the enrichment of REY in pelagic sediments.

Into the deep: Exploring the molecular mechanisms of hyperactive behaviour induced by three rare earth elements in early life-stages of the deep-sea scavenging amphipod Tmetonyx cicada (Lysianassidae)

With increasing socio-economic importance of the rare earth elements and yttrium (REY), Norway has laid out plans for REY mining, from land-based to deep-sea mining, thereby enhancing REY mobility in the marine ecosystem. Little is known about associated environmental consequences, especially in the deep ocean. We explored the toxicity and modes of action of a light (Nd), medium (Gd) and heavy (Yb) REY-Cl3 at four concentrations (3, 30, 300, and 3000 μg L−1) in the Arcto-boreal deep-sea amphipod Tmetonyx cicada. At the highest concentration, REY solubility was limited and increased with atomic weight (Nd < Gd < Yb). Lethal effects were practically restricted to this treatment, with the lighter elements being more acutely toxic than Yb (from ∼50 % mortality in the Gd-group at dissolved 689–504 μg L−1 to <20 % in the Yb-group at ca. 2000 μg L−1), which could be a function of bioavailability. All three REY induced hyperactivity at the low-medium concentrations. Delving into the transcriptome of T. cicada allowed us to determine a whole array of potential (neurotoxic) mechanisms underlying this behaviour. Gd induced the vastest response, affecting serotonin-synthesis; sphingolipid-synthesis; the renin-angiotensin system; mitochondrial and endoplasmic reticulum functioning (Gd, Nd); and lysosome integrity (Gd, Yb); as well as the expression of hemocyanin, potentially governing REY-uptake (Gd, Yb). While Nd and Yb shared only few pathways, suggesting a link between mode of action and atomic weight/radius, almost all discussed mechanisms imply the disruption of organismal Ca-homeostasis. Despite only fragmental genomic information available for crustaceans to date, our results provide novel insight into the toxicophysiology of REY in marine biota. The neurotoxic/behavioural effects in T. cicada at concentrations with potential environmental relevance warn about the possibility of bottom-up ecological consequences in mining exposed fjords and deep-sea ecosystems, calling for follow-up studies and regulatory measures prior to the onset of REY mining in Norway.

Uptake time and enrichment mechanism of rare earth elements in deep-sea bioapatite

Bioapatite is widely recognized as the primary carrier for rare earth elements and yttrium (REY) in deep-sea REY-rich muds. The incorporation of REY into bioapatite occurs at the water-sediment interface, which has the potential to serve as a proxy for reconstructing paleoenvironmental conditions. The timing of REY uptake and the fractionation of rare earth elements (REEs) within bioapatite are crucial factors to understanding the application of these proxies. In this study, we present in-situ geochemical data for bioapatite obtained from surface sediments in the high sedimentation rate Somali Basin of the northwestern Indian Ocean (NWIO), as well as fish teeth within nodules from the low sedimentation rate in the northwestern Pacific Ocean (NWPO). Our findings indicate that the uptake time of REY occurred rapidly, with the ΣREY content reaching 7265 μg/g in bioapatite from the surface sediments in the NWIO within several thousand years. The bone fragments exhibited a high ΣREY content, which was primarily attributed to substitution processes. This led to a notably elevated proportion of middle rare earth elements (MREE) compared to fish teeth. In contrast, the adsorption and substitution mechanisms responsible for REY incorporation decreased from the root to the tip in fish teeth, resulting in a pronounced decline in ΣREY content. The adsorption mechanism was identified as the primary process responsible for REY uptake in the fish teeth within the studied nodules from the NWPO. The fractionation pattern of REEs in these teeth exhibited similarities to that of fish teeth from the NWIO. Therefore, we inferred that the fish teeth within the studied nodules may preserve the original information during late diagenesis. The variation of REY contents in the nodules was influenced by the redox environment, and there is no evidence to support the migration of REY from the nodules into the fish teeth.

Insights on the formation of layered ferromanganese precipitates from the southern Mariana Arc, West Pacific, from micron-scale major, minor, and trace element variations

A combined laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy dispersive X-ray spectroscopy (EDS) study was used to map 49 elements in four FeMn precipitates produced from three different genetic processes (hydrogenetic, hydrothermal, and mixed-type hydrogenetic-hydrothermal) in samples obtained from the southern Mariana Arc. Results show Mn-oxide minerals are consistently found to be associated with Ba, Mo, Sb, V, Zn, and the rare earth elements and yttrium (REY), excluding Ce, whereas Fe-oxyhydroxide minerals are primarily associated with Ti, Co, Cr, Cu, Nb, and Pb. Element distributions in FeMn precipitates from the southern Mariana Arc differ from deposits formed in other environments; notably, there is a decoupling of As and Sb, and redox-sensitive elements are more variable than non-redox-sensitive elements. Samples previously classified as either hydrogenetic or hydrothermal in origin, based on bulk geochemical data, show characteristics of both at higher resolution. Combining high resolution in-situ data with genetic classification discrimination diagrams reveals more ambiguity in metal and metalloid origin than previously thought. Mariana Arc FeMn precipitates can be separated into two formation sub-types (hydrothermal or mixed hydrothermal/hydrogenetic) based on textural and compositional differences, e.g., differences in Ce/Ce and Y/Ho values and relative variations in (Zr + Y + Ce) versus (Co + Ni) versus (Mn + Fe). Improved classification and knowledge of how fast-growing hydrothermal FeMn precipitates form may help us identify a relatively renewable critical metal resource.

Vital effects and the fractionation of rare earth elements and yttrium during uptake by and transfer within freshwater bivalves and their shells

Mussels are commonly used as bioarchives in environmental monitoring, yet the impact of vital effects on the trace element or isotope ratios used as biogeochemical proxies is often only ill constrained. A prime example of such trace elements are the Rare Earth elements and Yttrium (REY) which have become (micro)contaminants in freshwater systems worldwide. We here report on the distribution of REY in different soft tissues and in the shells of freshwater bivalve A. anatina, commonly known as “duck mussel”, from the Danube River in Hungary and the Vistula River in Poland. Both rivers are contaminated with anthropogenic Gd from contrast agents used in magnetic resonance imaging (MRI). Regardless of the mussels' origin, all of their compartments show very similar shale-normalised REY patterns. None of the samples show any anthropogenic Gd anomaly, implying that in freshwater anthropogenic Gd from MRI contrast agents is either not bioavailable or that REY from ambient river water are insignificant for the REY budget of freshwater mussels. Compared to ambient water, the bivalves bioaccumulate the REY with preferential uptake of Ce and of light REY over heavy REY. However, REY concentrations in mussels are similar to or lower than those in their potential food source, with minor fractionation along the REY series besides slight preferential uptake of La and Y. Comparison of shells and tissues reveals the systematic oxidative decoupling of Ce from its REY neighbours, probably due to the presence of Ce(IV) solution-complexes in the mussels' extrapallial fluid. Despite possible REY fractionation during their initial uptake, vital effects do not impose any major control on REY fractionation during REY transfer within the mussels or during formation of their shells. Mussel shells may, therefore, conveniently be used for environmental monitoring of REY without major disturbance from vital effects.

Hydrogeochemical and rare earth element properties of geothermal waters and the use of abandoned oil wells in Diyarbakır

Türkiye is one of the most tectonically active regions in the world. Diyarbakır, which was chosen as the study area, is located in the south-eastern Anatolian region of Türkiye and also in the south of the Bitlis-Zagros Suture Zone (BZSZ). Some of the geothermal resources in Diyarbakır are actively exploited. The temperature of Çermik geothermal waters was recorded at 40–51 °C by MTA (General Directorate of Mineral Research and Exploration) between 2010 and 2014. However, subsequent measurements conducted following the Kahramanmaraş earthquake (Mw: 7.7 on 6 February 2023) revealed that the surface temperature of geothermal fluids had increased to between 52 and 56 °C. Previous studies have indicated that there are also many abandoned oil wells in the region where the wellhead temperatures are around 107 °C. As a result of hydrogeochemical analyses, deep circulating geothermal waters such as Çermik have Na-HCO3 composition, while shallow circulating and mixed cold surface waters such as Çınar, Bismil and Sur have Na-Ca-Cl-HCO3 composition. According to the chalcedony geothermometer results, the reservoir temperatures in the study area vary between 90 °C and 173 °C. REY (Rare Earth Elements and Yttrium) results show that geothermal fluids in the study area have negative cerium (Ce), europium (Eu) and yttrium (Y) anomalies. The negative Ce anomaly indicates that the colder aquifers are close to oxygen-rich surface waters and thermal fluids interact with Karacadağ volcanic rocks. Eu anomalies in groundwater are controlled by preferential mobilisation of Eu2+ during water-rock interaction compared to Eu3+, and negative Eu anomalies indicate leakage of geothermal fluids from granites. The Y/Ho values of the thermal fluids in the study area are between 30 and 40. This value is due to the active contribution of fluorine during the mobilisation of REY as a fluoride or fluorocarbonate ligand complex, causing Y to behave as a heavy pseudolanthanide. δ18O and δ2H isotope values show that the geothermal waters in the study area are of meteoric origin. The obtained results reveal that Diyarbakir province has a geothermal potential and usage potential can be increased by using the abandoned oil wells.

Mineralogy and Geochemistry of Rare Earth Elements in Carboniferous-Permian Coals at the Eastern Margin of the Ordos Basin.

This article used Carboniferous-Permian coals from the Jungar, Hedong, and Weibei Coalfields in the east of the Ordos Basin as research samples. Characteristics of coal quality, petrology, mineralogy, and geochemistry were analyzed by proximate analysis, inductively coupled plasma mass spectrometry, X-ray fluorescence spectroscopy, X-ray diffraction analysis, scanning electron microscopy-energy spectrum analysis, and incident light microscope. The enrichment regulations, distribution patterns, and occurrences of REY (rare earth element and yttrium) in coal under different geological conditions were compared. Geological significance and the influence of REY were then discussed. The average REY of Permian coal in the eastern margin of the basin is 127.9 μg/g, CC = 1.87, and the average REY of Carboniferous coal is 117.49 μg/g, CC = 1.72, which are within the normal enrichment range. The inorganic affinity of REYs in the study area is strong and mainly occurs in clay minerals and detrital phosphates and correlates well with LREY. The Permian coal sedimentary environment is more oxidized than the Taiyuan formation, and the Carboniferous coal sedimentary environment is noticeably more affected by marine water. With an increasing degree of coalification, the concentration of rare earth elements (REE) in high-rank coal vitrinite is lower than that in inertinite. In contrast, the concentration of REEs in low-rank coal is the opposite. This is because the oxygen-containing functional groups that can combine with REEs in vitrinite reduce significantly, resulting in the loss of trace elements into other forms. The provenance of the northern and central regions of the study area is mainly sedimentary rocks, granite, alkaline basalt, and continental tholeiite, while the southern region is mainly granite and sedimentary rocks.

Weathering-induced organic matter enrichment in marine-continental transitional shale: A case study on the early Permian Taiyuan Formation in the Ordos Basin, China

A comparative analysis of the factors controlling organic matter (OM) enrichment between marine-continental transitional (transitional hereafter) and marine or lacustrine shales is lacking. The early Permian Taiyuan Formation in the Ordos Basin, deposited during a shift from marine to continental settings in northern China, provides a unique opportunity to unravel the differences in OM enrichment mechanisms among these shales. The Taiyuan Formation is characterized by high TOC content (average 4.50%) and kerogen type II2-III. Most samples are thermally mature with a few high to post-mature samples relating to the Late Jurassic–Early Cretaceous Yanshanian magmatism. Rare earth elements and yttrium (REY) are dominated by light- and medium-types enrichments, with distinctly positive Gd anomaly, likely due to seawater incursion. A warm and humid climate prevailed during deposition of the Taiyuan Formation, consistent with the tropical-subtropical location of the North China Plate in the early Permian. The climatic conditions promoted intense continental weathering as reflected by high Th/Sc ratios, chemical index of alteration values, and feldspar alteration to scaly kaolinite. The V/(V + Ni) ratio is inconsistent with the other redox proxies, presumably due to variations in the redox buffer supply in the transitional facies (e.g., OM and pyrite), varying burial rates and dissimilar redox potential of different elements. Hence, this proxy should be interpreted with caution in such settings. Most redox proxies indicate oxic bottom water during deposition of the Taiyuan Formation transitional shale, in contrast to typical OM enriched marine and lacustrine shales where redox stratification or euxinic conditions are common. Instead, the dominant factor for OM enrichment in transitional shales appears to have been a high influx of terrestrial weathering products, including abundant higher-plants OM, associated with preservation of OM due to rapid burial. This process minimizes the detrimental effects of oxic conditions on OM accumulation in the transitional shale facies. This mechanism may hold relevance for analogous basins elsewhere.

Rare earth element enrichment process of bioapatite in deep-sea REY-rich sediments

Rare earth element and yttrium (REY) compositions of bioapatite (e.g., fish tooth and bone) can serve as potential paleoceanographic indicators. However, the REY enrichment of bioapatite and REY transfer from FeMn micronodule to bioapatite remain unclear owing to a lack of comparative study on these processes under variable redox conditions (oxic vs. suboxic), which hampers the utility of these indicators. To address these uncertainties, we conducted in situ geochemical analyses of fish teeth and FeMn micronodules from two REY-rich sediment cores (GC01 and GC02) collected from the Clarion–Clipperton fracture zone in the central equatorial Pacific. We found that the Ce/Ce* ratios of fish teeth from GC01 (sediments ΣREY = 723 ± 274 ppm) and GC02 (sediments ΣREY = 506 ± 65 ppm) gradually increased with depth under oxic conditions, with calculated oxic pore water-derived REY increasing from ∼0–3% on the surface to ∼11–24% at 200 cmbsf. In deep sediment columns (>200 cmbsf), the suboxic pore water contributed a small amount of REY (∼4% to ∼13%) to fish teeth, as evidenced by sharp increases in Ce/Ce* ratios of fish teeth and decreases in Ce/Ce* ratios and increases in YN/HoN ratios of micronodules. Therefore, the REY-patterns of fish teeth in core-deep samples were overprinted by oxic–suboxic pore waters may be unreliable archives of ancient bottom seawater.

Rare earth elements and yttrium (REY) in fjord waters: Comparison between seawater in the Trondheimfjord (Norway), its local riverine REY sources and the North Atlantic

The rare earth elements and yttrium (REY) are critical resources increasingly released into the environment due to their pivotal role for an ever-growing number of high-tech products and processes. Fjords, worldwide and particularly in Norway, are not only of high importance for biodiversity but they also have great economic value. Knowledge on the distribution of REY in Norwegian coastal and riverine waters is, however, surprisingly scarce. We here report REY data for water samples from depth profiles from ten stations in the Trondheimfjord, one of Norway’s largest fjords, several Norwegian rivers, and two wastewater treatment plants in Trondheim.Our results show that water from different locations in the Trondheimfjord yield similar REY concentrations that correlate well with dissolved organic carbon. The deepest sample at each station shows the lowest REY concentrations. The shale-normalised (SN) REY patterns of the fjord waters resemble those of North Atlantic seawater, but can be distinguished from open-ocean water by the smaller fractionation between light and middle REY (PrSN/TbSN ≥ 0.5). Stations in the vicinity of a river mouth show considerably higher REY concentrations at shallow depths. The respective REYSN patterns resemble the typically flat patterns of boreal rivers that are often rich in nanoparticles and colloids (NPCs). The REYSN patterns of the four rivers investigated (Nidelva, Orkla, Gaula, Stjørdalselva) show the features of the shallow(er) fjord water samples but have even higher REY concentrations. Ultrafiltration (< 1 kDa) data for the Nidelva corroborate that the typical “REYSN seawater signature” is in fact already present in freshwater where it is, however, usually hidden by the REY associated with NPCs. The local wastewater treatment plants release anthropogenic Gd (from contrast agents used in magnetic resonance imaging) into the Trondheimfjord, but this signal is immediately diluted and thus is not observed in the REYSN patterns of the fjord water. However, our results in general suggest that the slightly elevated Gd/Tb ratios observed in almost all fjord waters relative to North Atlantic marine water may rather be due to the presence of anthropogenic Gd in the southern North Sea and the Baltic Sea, corroborating that anthropogenic Gd can be applied as a sensitive far-field watermass tracer.

Genesis of Carboniferous aluminous-bearing strata in the northern part of the North China Craton: A case study of the Xingxian bauxite deposit

More than five billion tons of karstic bauxites were formed in the North China Craton (NCC) during the Late Carboniferous period. Compared to the bauxite ore, the genesis of the entire aluminous-bearing strata has received less attention. In this study, we conducted geological, mineralogical, and geochemical analyses on core samples from the aluminous-bearing strata located in Xingxian area, situated within the northern NCC, aiming to elucidate the genetic process of these formations. The aluminous-bearing strata consist of a bauxite layer (diaspore–anatase–kaolinite–florencite) sandwiched between the upper sandy claystone horizon (kaolinite–illite–quartz) and the lower berthierine-bearing claystone horizon (berthierine–diaspore–hematite–goethite). Based on the upper continental crust-normalized patterns of rare earth elements and yttrium (REY), immobile trace element ratios, mineral inheritance diagrams, and previous findings, it is suggested that the lower berthierine-bearing claystone was weathered from the impure limestone at the bottom, whereas the upper bauxite and sandy claystone mainly originated from intermediate-felsic igneous rocks of the northern margin of the NCC, granite from the North Qinling Orogenic Belt, and aluminosilicate rocks of the surrounding paleo-uplifts. During the early diagenetic stage, the berthierine was transformed under alkaline and reducing conditions from iron-rich clays (composed of clay minerals, ferric minerals, etc.) formed in acidic and oxidizing conditions from the underlying impure limestone. The coexistence of berthierine with low-temperature stability and diaspore is observed in the berthierine-bearing claystone, which precludes a high-temperature origin of diaspore in the aluminous-bearing strata. Moreover, diaspore is characterized by a small crystal size and is usually poorly crystallized, suggesting a supergene precipitation-diagenesis origin. The paragenetic minerals assemblages (e.g., diaspore, berthierine, goethite, hematite, etc.) suggest that the aluminous-bearing strata primarily formed in a transition zone nearer to the phreatic environment. Large-scale volcanism and warm, humid climatic conditions accelerated the decomposition of allochthonous weathering materials, resulting in the downward migration of metal ions. These ions then precipitated in a reducing and weakly alkaline environment, giving rise to form bauxite ore dominated by diaspore, anatase, and REY minerals.

Oxygen and sulfur stable isotope ratios of Late Devonian vertebrates trace the relative salinity of their aquatic environments

Late Devonian aquatic environments hosted the fin-to-limb transition in vertebrates. Upper Devonian (ca. 365−360 Ma) strata in Pennsylvania, USA, preserve a diversity of fishes and tetrapods in coastal marine to fluvial depositional environments, making this region ideal for investigating the ecology and evolution of Late Devonian vertebrates. A key unresolved issue has been reconstructing the specific aquatic habitats that hosted various vertebrates during this period. Specifically, the salinity of environments spanning fresh to shallow marine water is difficult to discern from sedimentological and paleontological analyses alone. Here, we analyze rare earth elements and yttrium (REY) as well as stable oxygen and sulfur isotope compositions (δ18O, δ34S) in fossil vertebrate bioapatite from late Famennian (ca. 362−360 Ma) strata of the Catskill and Lock Haven formations in the Appalachian Basin, USA, to determine the relative salinity of their aquatic environments. These results confirm the ecological euryhalinity of several taxa (Bothriolepis sp., tristichopterids, and Holoptychius sp.). Our results are the first demonstrating that some early tetrapod species occupied unequivocally freshwater habitats by late Famennian time (ca. 362−360 Ma). Our study shows that integrating sedimentological and paleontological data with combined oxygen and sulfur isotope analysis allows precise tracing of the relative salinity of vertebrate habitats deep in the past.

Surface water oxygenation and low bioproductivity during deposition of iron formation of the Jacadigo Group (Brazil): Insights from combined cadmium – Chromium isotopes

The Banda Alta Formation (Urucum district, Mato Grosso do Sul, Brazil) comprises ∼600 Ma Fe and Mn deposits, which are among the world's youngest and largest Neoproterozoic sedimentary Fe and Mn formations (IF; MnF). These have been deposited in a redox-stratified, marine sub-basin (Jacadigo Basin), which was strongly influenced by glacial advance/retraction cycles with temporary influx of continental freshwater and upwelling of metal-enriched deep anoxic seawater. Cr and Cd isotopes measured on meticulously separated hematite mesobands from drill core samples are relatively homogenous throughout the ca. 325 m thick sequence sampled in the Banda Alta Fm., with average authigenic δ53Cr values of +0.93 ± 0.24 ‰ (2σ; n = 23) and δ114Cd values of −0.14 ± 0.14 ‰ (2σ; n = 15). The significant enrichment of Cr, in parallel with the strong enrichments of other redox sensitive elements (U, Mo), attests for effective and efficient reduction removal processes in the surface waters during cycles where upwelling Fe2+-rich waters reached the oxygenated surface layer exposed to the atmosphere during episodic glacier retreat stages. Assuming a similar quantitative and efficient removal pathway of dissolved Cd by iron oxyhydroxides, the so-inferred average δ114Cd signature of −0.14 ± 0.14 ‰ in the Jacadigo Basin surface water is significantly lower than signatures of modern ocean surface waters with a range of δ114Cd of ca. ∼0.4 to ∼1 ‰ and even lower than the signature of modern ocean deep waters with δ114Cd of ∼0.3 ‰. It possibly attests to reduced primary production levels and lower nutrient utilization rates during deposition of the Late Neoproterozoic Jacadigo Group, compared to today. This despite the inferred oxidized surface water layer that must have prevailed during this time, as implied by the strongly positively fractionated Cr isotope signatures and pronouncedly negative Ce-anomalies recorded in the seawater-like, shale-normalized Rare Earth Element and Yttrium (REY) patterns exhibited by the hematite mesobands. Data presented herein speak for: (1) a stable, isotopically heavy Cr input to the Jacadigo Basin at the time of deposition, implying high atmospheric O2 levels in the Late Neoproterozoic (2) likely quantitative, reductive incorporation / adsorption processes of dissolved Cr and Cd, respectively, into/onto precipitating iron oxyhydroxides, and (3) the prevalence of low nutrient concentrations and utilization rates in the Jacadigo Basin during glacier retreat cycles. Banded iron formations are considered suitable archives for reconstructing redox and bioproductivity levels in past marine depositional basin, including those prevalent in Neoproterozoic glacial conditions, via employing the CrCd isotope double tracer to iron-rich mesobands.

Study on the material source and enrichment mechanism of REE-rich phosphorite in Zhijin, Guizhou

Rare earth element (REE)-rich phosphorite in the Guizhou region mainly exists in the Doushantuo Formation and Gezhongwu Formation in early Cambrian strata, which are some of the important strata containing phosphorite resources in China. The early Cambrian Zhijin phosphorite in Guizhou Province, China, has high rare earth element and yttrium (REY) contents of up to 2500 ppm, with heavy REY (HREY) contents accounting for ~ 30% of the total REY contents. However, the specific controlling source and environment of phosphorite (especially the REEs in Zhijin phosphorite) are still unsolved. Through field geological investigations; mineralogical, geochemical, Sr–Nd isotope analyses; and tectonic characteristics, the material source, sedimentary environment and seawater dynamics of REEs in phosphorite are studied. It is considered that the REEs enriched in the Zhijin phosphorite are mainly affected by precipitation from hydrothermal fluid. Moreover, from the late Ediacaran to the early Cambrian, the depositional environment from the bottom to the top of the water tended to be hypoxic, and the activity of hot water fluid tended to be strong. The change in redox conditions is closely related to the rise and fall of sea level. Combined with the tectonic background, these results show that the weakly oxidized environment may be an important factor controlling the enrichment of REEs. The enrichment of REEs may be closely related to volcanic hydrothermal activity, later diagenesis and seawater dynamics.

Petrography and stratigraphic Os isotopic ages of ferromanganese nodules from the Northwest Pacific east of Minamitorishima Island

The area offshore of Minamitorishima Island, Northwestern Pacific Ocean, contains large amounts of seafloor mineral resources such as ferromanganese (Fe–Mn) nodules, Fe–Mn crusts, and rare-earth element and yttrium (REY)-rich muds. In this study, we applied stratigraphic Os isotopic dating to a Fe–Mn nodule for the first time to date its formation/depositional age, and mineralogical and texturally characterized a complementary nodule. Based on macroscopic and microscopic observations, the studied Fe–Mn nodules can be divided into three layers: Layers L2, L1, and L0 from core to rim. Under the microscope, the Fe–Mn nodules are dominated by vernadite and Fe-oxyhydroxide. In particular, Layer L1 is dominated by banded-columnar vernadite and contains lower amounts of clay minerals derived from the detrital component than Layers L2 and L0. The bulk major and trace element geochemical compositions of sampled layers in the Fe–Mn nodules all plotted in the hydrogenous field in several discrimination diagrams. The Os isotopic ages determined by fitting to the paleo-seawater 187Os/188Os curve can be divided into three clusters (35.7–31.0, 19.0–9.0, and 4.0–1.0 Ma, corresponding to Layers L2, L1, and L0, respectively). These Os isotopic ages indicate that two periods of very slow growth or growth hiatuses occurred during the formation of the Fe–Mn nodule; these age gaps are related to the intermittent (discontinuous) timings of the beginning of Fe–Mn nodule formation offshore Minamitorishima Island.

Geological features of the Zn-Pb prospect in the Bou-Izourane district (Morocco)

The Zn-Pb mineralization in the Bou-Izourane district, located in the High Atlas Mountains of Morocco, contains estimated reserves of 40 200 tons of ore with an average grade of 20% Zn and 3.5% Pb. It is developed on N–S to NNW–SSE-trending faults that cut Liassic carbonate marl deposits. The paragenetic mineral sequence consists of galena, sphalerite and late-stage calcite. Oxidation phases of galena into cerussite and sphalerite into smithsonite are common in the Bou-Izourane ore, linked to the infiltration of meteoric waters and the oxidation of these sulphides. The Zn-Pb mineralization runs parallel to the fluorite veins associated with the igneous rocks of Tamazeght, but no petrographic or field relationship has been demonstrated between these two mineralizations (i.e., Zn-Pb and fluorite). The distribution of rare earth elements and yttrium (REY) in the Zn-Pb mineralization of Bou-Izourane shows a notable similarity with the Mississippi Valley Type (MVT) mineralization of the Central High Atlas of Morocco, although the concentrations more closely resemble those of REY in fluorite linked to the magmatic-hydrothermal activity of Tamazeght. However, the analysis of their distribution in post-fluorite calcite and post-Zn-Pb calcite reveals a strong concordance, suggesting that these two calcites are associated with the same phase and have a common origin. The classification of the Zn-Pb prospect in Bou-Izourane remains controversial, fluctuating between an MVT-type mineralization, similar to most Zn-Pb mineralizations in the Central High Atlas of Morocco, and a mineralization linked to the magmatic-hydrothermal activity of Tamazeght, which could provide heat and metallogenic material. Characterizing the Zn-Pb ore of Bou-Izourane is crucial for the future exploration of zinc and lead deposits in the High Atlas of Morocco and could advance the development of Zn-Pb mining in the region, from artisanal exploitation to professional mining

Enrichment of Smectite in the REY‐Rich Mud of the Clarion‐Clipperton Fracture Zone in the Eastern Pacific and Its Geological Significance

AbstractREY‐rich mud, consisting of deep‐sea sediments with high concentrations of rare‐earth elements and yttrium (REY), holds significant economic potential. Many studies have been conducted on biogenic apatite, ferromanganese micronodule, and phillipsite within these deposits to ascertain the REY enrichment mechanisms. However, the knowledge of clay minerals in REY‐rich mud, which is the predominant component of pelagic sediments, is still limited. In this study, two adjacent gravity cores (core GC02: REY‐rich mud; core GC03: typical sediments of equatorial Pacific) were collected from the Clarion‐Clipperton Fracture Zone (CCFZ) of the Eastern Pacific to study the role of different clay minerals in REY enrichment. The clay minerals in core GC03 and core GC02 are primarily illite (averaging 60%) and smectite (averaging 63%), respectively, and the smectite in core GC02 was mainly Fe‐rich, which was probably formed via the reaction between opal and FeOOH. Moreover, multiple studies have reported similar smectite enrichment in REY‐rich mud, suggesting that it is a common characteristic. The presumed hydrothermal or volcanic origination of smectite in REY‐rich layers of core GC02 indicates the essential role of hydrothermal and volcanic activities in REY‐rich mud formation during the Oligocene in the western CCFZ.