Rare Earth Element Patterns Research Articles

Extracting Meaningful Environmental and Age Information From a c. 2.4–2.2 Ga Peritidal Phosphorite: The Turee Creek Group, Western Australia

AbstractPhosphorites can record oceanic conditions during their deposition, but the faithful retention of primary information in Paleoproterozoic deposits can be mitigated by post‐depositional processes. Here, we examine a peritidal phosphorite within a microbialite reef complex in the 2.4–2.2 Ga Turee Creek Group in Western Australia to assess the environmental information retained. Field mapping and petrography distinguishes between authigenic and locally transported phosphorite fragments, each of which contains unique information regarding the deposit. Elemental mapping and laser‐ablation analyses differentiate the impact of depositional versus early diagenetic versus metamorphic processes within these fragments. Samples within a near‐shore pebble conglomerate have mixed riverine‐oceanic signals and lack cerium anomalies, consistent with the depositional environment. Clasts from off‐shore peloidal grainstone beds retain “hat‐shaped” patterns with small negative cerium anomalies, reflective of transport and redeposition within potentially oxic seawater. U‐Pb isotopic dates range from ∼1.8 to 2.3 Ga and are generally uncorrelated with rare earth element and yttrium data. The youngest date (∼1.8 Ga) is associated with recrystallized apatite, with concave down, middle rare earth element enriched patterns. A potential depositional age, ∼2.3 Ga, is associated with massive apatite in a chert‐rich clast that has rare earth element patterns reflective of riverine‐oceanic signals. Overall, the peritidal system in the reef was dynamic, with potentially oxic seawater that had a strong riverine influence. Local recycling and reworking, early diagenesis, and later orogenic events impacted the preserved geochemical signals and together show that spatially resolved geochronological and geochemical data are ideal for interpreting ancient phosphorites.

Trace element geochemistry of sediments in the Pearl River Estuary and its implication for provenance

The Pearl River system is China’s third longest river and the Pearl River Estuary is a major estuary in China. In the paper, a sediment core collected from the coastal zone in the Pearl River Estuary was analyzed for trace element concentrations and grain size to identify provenance during the past decades. In addition, the tectonic framework of the study area has also been studied using reliable geochemical tracers, including rare earth elements (REEs) and trace elements. The results reveal a significant contribution of reworked sediment from multiple sources. Discrimination diagrams suggest that the sediments display felsic characteristics with recycled components, and therefore, the source rock types of the sediments are presumed to be granitic rocks. The REE patterns observed in the samples primarily reflect the influence of an ancient continental crust that contains felsic materials on the sediments with an LREE/HREE ratio of 7.94–9.56 (mean 8.46) and a δ Eu value of 0.61–0.70 (mean 0.65). The sediments are plotted into a zone of continental island arcs, which was formed during the late Mesozoic subduction of the ancient Pacific. The study on the source of sediment cores shows that the main source of sediments in this area excludes the possibility of the upper middle river from the Pearl River Watered, which reflects the importance of the lower Pearl River Basin, especially the Dongjiang River, for material transport in the study area. Our results demonstrate that the geochemical characteristics of trace elements in sediment could provide an efficient approach to identify sediment provenance in estuaries worldwide.

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 (<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.

Petrogenesis and Geodynamic Implications of Cretaceous Nb-Enriched Mafic Dykes in the East Kunlun Orogen, Northern Tibet Plateau: Constraints from Geochronology, Geochemistry and Sr-Nd Isotopes

There is a magmatic lull period in the East Kunlun orogen (EKO) during the Jurassic to the Cretaceous. However, due to the lack of records of magmatic activity restricts our understanding of the late Mesozoic magmatic-tectonic evolution of the EKO. Herein, an integrated study of geochronology, whole-rock geochemistry and Sr-Nd isotopes were conducted for the Cretaceous mafic dykes in the EKO, Northern Tibet Plateau, to reveal their petrogenesis and geodynamic implications. LA-ICP-MS Zircon U-Pb dating reveals that the studied mafic dykes comprising diabase and diabase porphyry emplaced at ca. 80.9 ± 0.8 Ma. The Cretaceous mafic dykes have low contents of SiO2 (46.36 wt.%~47.40 wt.%) but high contents of MgO (6.79 wt.%~7.38 wt.%), TiO2 (1.91 wt.%~2.13 wt.%), Nb (12.4~18.3 ppm) and Nb/U ratio (31~39), resembling Nb-enriched mafic dykes. They exhibit chondrite-normalized rare earth element (REE) and primitive mantle-normalized trace element patterns, remarkably similar but not identical to the oceanic island basalts (OIB). The moderate REE fractionation ((La/Yb)N = 3.55~5.37), weak negative Eu anomalies (δEu = 0.87~0.97) and relative enrichment of Rb, Ba, K, as well as high contents of Cr and Ni and slightly depleted Sr-Nd isotopes (εNd(t) = −0.18~1.33), suggest that the studied dykes originate from a partial melting of spinel lherzolite and a little of garnet which was previously modified by subducted sediments. Combined with other evidence, we propose that the studied Cretaceous Nb-enriched mafic dykes in the Northern Tibet Plateau were formed in the intraplate setting, which may be a partial melting of the enriched mantle in the lower lithosphere caused by the activity of the East Kunlun strike-slip fault.

Petrology of the Cretaceous Riacho do Cordeiro dike swarm: Unraveling the giant low-Ti tholeiitic plumbing system of the Equatorial Atlantic Magmatic Province

The formation of the Early Cretaceous Equatorial Atlantic Magmatic Province (EQUAMP), northeastern Brazil, is related to the fragmentation of the West Gondwana supercontinent that culminated in the separation of South America and Africa, during the Lower Cretaceous. The EQUAMP is characterized by its intrusive nature, where mafic dike swarms intrude the Proterozoic basement of the Borborema Province. The other components of this province are represented by sill complexes hosted between the Paleozoic sediments in the Parnaíba Basin, described as the Sardinha Formation. The magmatism related to the EQUAMP is tholeiitic, with high-Ti, and low-Ti magmas compositions that with similar features that are observed in other Mesozoic igneous provinces of Gondwana. The Riacho do Cordeiro dike swarm (RCo) represents the southernmost manifestation of the EQUAMP, consisting of a series of igneous bodies aligned along the N45E trend, arranged in an en echelon pattern. This structure extends for about 350 km, cutting the Precambrian basement of the southern segment of the Borborema Province. The dikes have a composition similar to tholeiitic basalts and basaltic andesites, but they are distinguished from the other components of the EQUAMP by their exclusively low-Ti content (TiO2 = 1.7–1.2 wt%). Magmatic differentiation is the main petrogenetic mechanism of the low-Ti magmas, typified by the systematic fractionation of major elements with respect to the variation of MgO (6.4–2.4% wt%). Trace (including rare earth) element patterns show enrichment in incompatible elements and negative anomalies in NbTa, a pattern recognized in continental basalts derived from (or contaminated with) lithospheric mantle. The Sr (87Sr/86Sr(i) 0.7072 to 0.7091) and Pb (206Pb/204Pb 18.360 to 18.785) isotopic signatures, combined with negative values for εNd(i) (−4.8 to −6.1) and TDM model ages >1.2 Ga, confirm the involvement of reservoir(s) in the upper mantle possibly modified by ancient subduction processes. The first reported 40Ar/39Ar ages for the low-Ti tholeiites of the RCo indicate ages from 134.53 ± 3.10 to 132.19 ± 1.28 Ma. Geochemically, the low-Ti tholeiites of the RCo are equivalent to low-Ti dikes that constitute part of the Rio Ceará Mirim dike swarm, the main component of the EQUAMP. Besides that, in a scenario external to this province, the same compositional correspondence is found within the Cretaceous dikes of the Vitória-Colatina swarm, southeastern Brazil, and the low-Ti type lavas of the Paraná-Etendeka Province. This compositional and geochronological connection between the tholeiitic magmatism located north and south of the São Francisco craton supports a possible genetic connection between these two Early Cretaceous LIPs and serve as base to future investigations that deal with what would have been the (global) mechanisms that led to the rifting of the Atlantic, from the southern segment to the equatorial margin.

Mineralogy and element geochemistry of the Bayan Obo (China) carbonatite dykes: Implications for REE mineralization

The Bayan Obo deposit in China is the world's largest rare earth element (REE) deposit. However, its genesis remains highly debated. It is considered to have a close genetic association with carbonatites because of the presence of nearby carbonatite dykes and the geochemical similarities between these dykes and the orebody. However, the evolution of these dykes and associated REE mineralization remain poorly understood, hindering the origin interpretation of the deposit. This study provides new insights into the petrography, mineralogy, and major- and trace-element geochemistry of these carbonatite dykes and rock-forming minerals to reconstruct the magmatic evolution and REE enrichment of the deposit. The dykes evolved from dolomite- to calcite-dominated (i.e., calcite and fenitized calcite) carbonatites, and their REE content remarkably increased, with the latter developing strong REE mineralization. The dolomites and minor calcites within the dolomite carbonatites exhibit a steep negative slope with high light REE (LREE) enrichment and heavy REE (HREE) depletion, similar to the whole rock. In contrast, the calcites from the calcite-dominated carbonatites exhibit flat REE patterns with HREE enrichment. Combined with previous isotopic data and our petrology, mineralogy, and geochemistry study, we propose that these rocks are derived directly from the low-degree melting of the underlying mantle source. REE mineralization may be related to the progressive crystallization of rock-forming calcites of calcite-dominated carbonatites. Monazite, bastnäsite, parisite, and huanghoite are the dominant REE minerals and exhibit intimate associations with barite and alkaline silicate minerals such as aegirine, biotite, K-feldspar, and albite. This assemblage indicates that the REE were primarily transported via REE–sulfate and REE–alkali complexes, with the latter favoring HREE, and the precipitation of alkaline silicate minerals destabilized these REE complexes, facilitating REE mineralization.

Concentration and distribution patterns of rare earth elements (REEs) in stream sediments of Pakistan

Currently, the metals of Rare Earth Elements (REEs) have become very critical to various modern technologies ranging from cell phones and televisions to LED light bulbs and wind turbines. This work was carried out as the Pakistani contribution to the National-scale Geochemical Survey of South and Central Asia (NGSSCA) project. The objective of this study was to document and study the amounts and distribution of REEs in stream sediment of Pakistan, where such national-scale geochemical mapping was launched for the first time. A total of 4277 regular and 168 duplicate samples were collected, encompassing approximately 360,000 km2 of Pakistani outcrop regions. The findings from the geochemical analysis of stream sediment in Pakistan revealed a spectrum in the total Rare Earth Elements (ΣREE) concentration, spanning from 10.22 mg/kg to 1403.1 mg/kg, averaging at 132.5 mg/kg. LREEs are relatively enriched compared to HREEs with an average of LREEs/HREEs of 3.08. The distribution patterns of REEs in stream sediment are demonstrated. It's has been concluded that high concentrations of REEs are mainly distributed in the Himalayan fold and thrust belt, the Karakoram terrane and the Kohistan island arc in the northern part of Pakistan. The bedrock mineralogy and lithology significantly affect the distribution patterns of REEs in stream sediments. The national geochemical mapping of Pakistan provides a useful method for locating alkaline igneous rocks and identifying potential REE mineralization.

Compositional analysis of Apollo 12 Granitic Breccia 12013: Insights into protoliths and formation

We report bulk rock composition and mineral chemistry of previously unstudied fragments and thin sections of lunar granitic breccia 12013. Instrumental Neutron Activation Analysis data on 25 fragments indicate that the 12013 breccia can be described as a three-component system comprising granitic, rare earth element (REE)-rich, and mafic components. The granitic component is low in FeO and REE but rich in K2O, Th, and associated incompatible elements. The REE-rich component has an elevated concentration of REE, moderate FeO, and low concentrations of those elements that are high in the granitic component, in other words, its composition is complementary to that of the granitic component. The mafic component is richest in FeO, and low in those elements that are concentrated in the granitic and REE-rich components. Petrographically, the REE-rich component is an impact melt breccia with a composition unique to Apollo 12 impact melt breccias. Trace-element concentrations in the REE-rich component indicate that its protolith is possibly monzogabbro, although its composition is significantly more magnesian than other known lunar monzogabbros. The mafic component is dominated by fine-grained pyroxene and plagioclase that appear to have recrystallized after impact. However, preserved lithic clasts with an igneous texture occur in the mafic component and are inferred to represent its protolith. The textures of the preserved mafic lithic fragments and lack of Mg-Fe zoning in pyroxene indicate that the protolith of the mafic component formed either as a crustal intrusion or at the bottom of a thick lava flow. The composition of the mafic component is unlike any previously studied mare basalt samples. Textures of this complex breccia suggest that the granitic breccia was first incorporated with the mafic component to form the “gray breccia”, and that the gray breccia was then incorporated with the REE-rich component while the components were still in a hot, plastic state. The complementary trace-element compositions, including the REE patterns, indicate that the petrogenesis of the granitic and REE-rich components are related. We infer that silicate-liquid immiscibility is likely not the formation mechanism for the 12013 components. Instead, bimodal volcanism owing to basaltic underplating may have led to the formation of the 12013 components.

Polymetallic tungsten skarn mineralisation related to the Periadriatic intrusion at Lienzer Schlossberg, East Tyrol, Austria

Abstract A regional tungsten anomaly was discovered and explored in the Lienzer Schlossberg area that is part of the crystalline Austroalpine nappe complex of the Eastern Alps in the 1970/80-ties. Tungsten is present as scheelite, which occurs in steeply SSW dipping WNW-ENE oriented quartz veinlets and joints within the porphyritic dioritic to tonalitic/granodioritic host rocks of the Oligocene Lienz/Edenwald intrusion and in the exoskarn, which developed at the contact of the intrusion with Ca-rich lithologies. The skarn system is characterised by two stages: (1) a primary high-temperature calc-silicate stage characterised by grossular, diopside-hedenbergite, vesuvianite, wollastonite and Ca-plagioclase and (2) a retrograde skarn stage including scheelite-bearing massive sulphide ores (pyrrhotite, chalcopyrite, tremolite-actinolite, diopside-hedenbergite) and scheelite-rich fault rocks with calcite, sericite and chlorite. The two ore stages, the mineral paragenesis and composition is like that of a reduced tungsten skarn; i.e., garnet is grossular-rich, clinopyroxene is diopside-hedenbergite. Vesuvianite contains up to 1.8 mass % fluorine. Scheelite has been studied by cathodoluminescence (CL), electron probe microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. Three types of scheelite (Scheelite 1–3) are distinguished. In short-wave UV light, all types show blue fluorescence but CL revealed internal micro-textures in scheelite grains which are dominated by oscillatory zoning. Prolonged hydrothermal activity is indicated by dissolution-replacement and overgrowth textures affecting the primary zonation and trace element composition of scheelite. The distribution of rare earth elements (REE) in Scheelite 1 in tonalite-hosted quartz veinlets shows a convex (i.e., middle REE-enriched), heavy REE-depleted pattern with negative Eu anomalies (EuA ). The evolution of REE patterns from skarn-hosted Scheelite 2 and 3 illustrates a gradation of convex REE patterns with high ΣREE and distinct negative Eu anomalies to relatively flat REE patterns with small to no EuA . Scheelite at Lienzer Schlossberg has one of the highest ΣREE+Y contents of all scheelite-bearing ore settings in the Eastern Alps but incorporates minor Mo and the least Sr. High Na and Nb contents together with the positive correlation of REE+Y vs. Na+Nb+Ta suggests that the main exchange vectors for REE incorporation in scheelite is via a combined coupled substitution mechanism. Results of this study confirm the genetic similarity with reduced tungsten skarns and highlight the tungsten potential of this area.

Origin and evolution of lithospheric mantle beneath the juvenile Arabian–Nubian Shield: Evidence from the Natash peridotite xenoliths, Southern Eastern Desert, Egypt

Compared with the Archean cratonic mantle, much less is known about the genesis and composition of the subcontinental lithospheric mantle (SCLM) beneath the juvenile terranes. In this study, we present petrology and mineral chemistry analyses of peridotite xenoliths carried by Cretaceous volcanics from the Natash area in the western Arabian–Nubian Shield (ANS). Combined with mantle xenoliths from the eastern ANS, we aim to constrain the nature, origin, and evolution of SCLM beneath the juvenile terrane. The Natash peridotite xenoliths, including well-preserved clinopyroxene (Cpx) and spinel (Sp), are categorized into two groups. Group A peridotites display exceptionally high Mg# (molar100 × Mg/(Mg + Fetotal)) in Cpx (95.6–96.7) and Cr# (molar100 × Cr/(Cr + Al)) in Sp (45.5–51.7), signifying a high degree of melting and refractory nature. Cpx in Group A demonstrates low Ti/Eu (532–1785) and high (La/Yb)N (5.34–26.29) ratios, indicative of carbonatitic metasomatism. Comparatively, Group B peridotites exhibit relatively high Mg# in Cpx (93.8–95.5) and Cr# in Sp (15.9–26.2), indicating a low degree of melting and fertile nature. Cpx trace element patterns subdivide Group B into three sub-groups. Cpx in Group B1 are characterized by high Ti/Eu (3934–5622) but low (La/Yb)N (0.91–2.98), implying silicate melt metasomatism. Both Groups B2 and B3 Cpx show steep rare earth element (REE) patterns, negative anomalies in high field-strength elements, and high (La/Yb)N (3.62–7.57). However, Cpx in B3 exhibit higher Ti/Eu ratios and water-soluble element contents than those in B2 peridotites. In addition, the spoon-shaped REE patterns are prominently unique to Cpx in Group B3. Hence, it is inferred that Group B2 were influenced by carbonatitic melts, whereas the evolved small-volume CO2-H2O-rich fluids infiltrated into Group B3 samples. Furthermore, the high Sr contents (71–404 ppm) but low 87Sr/86Sr (0.7003–0.7034) ratios of Cpx in Natash peridotites suggest that the various metasomatic agents all originated from the asthenosphere. Collectively, the Natash peridotite xenoliths exhibit similar nature and metasomatism processes with those from Cenozoic volcanics in the eastern ANS, and they all show affinity to continental peridotites. The pMELTS simulation suggests that the refractory peridotites have a high melting pressure (typically >3 GPa), while the fertile samples register a low melting pressure. Consequently, we infer that the SCLM beneath the juvenile ANS was formed through the cooling of upwelling asthenosphere, incorporating the ancient mantle fragments, and subsequently underwent asthenosphere-derived carbonatitic and silicate melt/fluid metasomatisms.

Neoproterozoic passive margin formation and evolution during the Rodinia–Gondwana supercontinent cycle at the eastern margin of the West African Craton

Abstract Petrographical and geochemical data from the Togo structural unit (TSU), also referred to as the Atacora structural unit, are presented together with the existing dataset; geochemical and age data from the sedimentary and metasedimentary rocks from the passive margin sequences of the Dahomeyide belt in Ghana to infer their provenance and depositional setting and expand the discussion on the Rodina–Gondwana supercontinent assembly during the Pan-African orogeny. The metasedimentary rocks of the TSU are quartzites and phyllites. The framework grains of the quartzites consisting dominantly of quartz and small amounts of feldspar grains and relict lithic fragments classify them as quartz arenite, subarkose and sublitharenite. Generally, the studied rocks show similar rare-earth element and multi-element patterns, which imply derivation from similar sources. Elemental ratios, including (La/Lu)N, Th/Sc and La/Sc, suggest sediments sourced from intermediate to felsic rocks. Provenance and depositional setting indicators of the TSU suggest deposition in a passive margin setting, with the West African and Amazonian cratons’ granitoids and granitic gneisses as possible provenance, akin to siliciclastic rocks of the Buem structural unit and the Voltaian Supergroup of the Volta Basin. The deformational history of the TSU is similar to those of the Buem structural unit and the eastern margin of the Voltaian Supergroup, indicating the effect of the Pan-African orogeny on the passive margin of the Dahomeyide belt. We, therefore, propose the formation and evolution of a Neoproterozoic passive margin unit, which was tectonically deformed during the Rodinia–Gondwana supercontinent cycle.

Rare Earth Element Characteristics of Shales from Wufeng-Longmaxi Formations in Deep-Buried Areas of the Northern Sichuan Basin, Southern China: Implications for Provenance, Depositional Conditions, and Paleoclimate.

To explore the sedimentary environment and the background of the source area of organic-rich shales in the Wufeng-Longmaxi Formations in the northern Sichuan Basin, samples from Well XX1 in the area were subjected to geochemical testing and analysis of organic carbon content, trace elements, and rare earth elements (REEs). The results show that the total content of REE (ΣREE) of the shale in the Wufeng-Longmaxi Formations varied from 183.08 to 234.66 μg/g with an average of 212.59 μg/g, which is significantly higher than the content of the North American shale composite. The fluctuations in the total amount of REEs in the shale of the Wufeng-Longmaxi Formations reflect certain differences in the geochemical conditions of the Upper Ordovician-Lower Silurian shale. The ratios of LREE/HREE, LaN/YbN, LaN/SmN, and GdN/YbN and the distribution of normalized REE patterns indicate that the source supply or sedimentary structural background may have changed during the shale deposition period of the Wufeng Formation, while the shale deposition period of the Longmaxi Formation may be in a relatively stable source supply and sedimentary structural background. There is no significant correlation between δCe and ΣREE, and the obviously negative Eu abnormity and the weak Ce abnormity indicated that the diagenesis had a limited impact on REEs. Geochemical parameters such as values of ∑REE, δEu, δCe, Ceanom, and LaN/YbN indicate that the climate during the Wufeng-Longmaxi Formation shale deposition period was warm and humid, and the shale was deposited mainly in the suboxic-anoxic water environment. The deposition rate was stable and slow, providing good conditions for the production and preservation of organic matter. At the same time, this shows that the water environment of Wufeng Formation is more anoxic and reductive than that of Longmaxi Formation, which is more conducive to the preservation of organic matter. The correlation between ΣREE and the content of Sc, Ti, Cr, Co, Zr, Nb, Th, Hf, Ta, and other elements indicates that the sources of REEs in the shale of Wufeng and Longmaxi Formations in the study area are similar, mainly terrestrial clasts, and some may come from the sea. The REE distribution pattern shows that the shale provenance of the Wufeng-Longmaxi Formations mainly comes from the upper crust. The La/Yb-∑REE diagram shows that the sediment-parent rocks are mainly early sedimentary rocks and these sediment-parent rocks have granite provenance characteristics. Compared to La/Yb, LREE/HREE, LaN/YbN, and other REE characteristic parameters, it is inferred that the tectonic background of the study area is dominated by passive continental margin.

Arc volcanism initiated on the eastern margin of Eurasia during the Early Cretaceous: Geochemistry of the Takanokura volcanic rocks in the Abukuma Mountains, Northeast Japan

AbstractThe Early Cretaceous Takanokura Formation in the eastern part of the Abukuma Mountains consists of a lower felsic ignimbrite and upper intermediate lavas and volcaniclastic rocks, representing the initial arc‐type in northeast Japan. In this study, I analyzed the major and trace element contents and Sr‐Nd‐Pb isotopic ratios of these eruptive products; then, I discussed their magma genesis based on their geochemical properties. Although igneous rocks of the same period in other localities of northeast Japan are characterized by the occurrence of adakites, these volcanism are composed of non‐adakitic high‐ to medium‐K andesite to rhyolite that are rich in large‐ion lithophile elements and poor in high‐field‐strength elements and have low Sr/Y values and flat heavy rare earth element patterns. Furthermore, these rocks have high radiogenic Pb isotopic ratios. The rhyolite and dacite have been thought to derive from crustal melting, whereas the andesite formed by the mixing of crustal felsic melts and mafic magmas generated by melting of the lithospheric mantle. Although previous studies attributed the formation of the Early Cretaceous adakites to the hot subduction of a mid‐ocean ridge, recent global plate motion reconstructions reject this model. To generate magma from a cold slab and lithospheric mantle that does not spontaneously melt, the mantle wedge under northeast Japan must have experienced heating. During this period, the volcanic province along the eastern margin of Eurasia expanded rapidly toward the trench, forming grabens. Therefore, I concluded that the advance of the hot asthenosphere into the forearc region that led to this expansion, which caused the retreat of the subduction boundary of the paleo‐Pacific plate to retreat and ultimately converted northeast Japan from an accretionary complex into a volcanically active region.

Rare Earth Element Variability in Italian Extra Virgin Olive Oils from Abruzzo Region.

Extra virgin olive oil is a food product from the Mediterranean area that is particularly and continuously experiencing to increasing instances of fraudulent geographical labeling. Therefore, origin protection must be improved, mainly based on its intrinsic chemical composition. This study aimed to perform a preliminary chemical characterization of Abruzzo extra virgin olive oils (EVOOs) using rare earth elements (REEs). REEs were evaluated in EVOO samples of different varieties produced in different geographical origins within the Abruzzo region (Italy) in three harvest years using ICP-MS chemometric techniques. Principal component, discriminant, and hierarchical cluster analyses were conducted to verify the influence of the variety, origin, and vintage of the REE composition. The results of a three-year study showed a uniform REE pattern and a strong correlation in most EVOOs, in particular for Y, La, Ce, and Nd. However, europium and erbium were also found in some oil samples. Compared with cultivar and origin, only the harvest year slightly influenced the REE composition, highlighting the interactions of the olive system with the climate and soil chemistry that could affect the multielement composition of EVOOs.

Recycled crustal components in the depleted mantle source: Evidence from Early Cretaceous mafic rocks in the southern margin of the North China Craton

Abundant subducted materials are recycled into the deep mantle during the plate subduction process and are further reflected in the postcollision mafic rocks. The Early Cretaceous Mid-Oceanic-Ridge-Basalt (MORB)-like mafic rocks in the southern margin of the North China Craton (SNCC) preserve significant information on recycled materials. These rocks provide a window for discussing the crust-mantle interaction and tracing the history of subduction. The studied rocks comprise the Jingwan metadiabase, Putaozhuang, Nianpanzhuang, and Niujiaowan metahornblende gabbro, with Early Cretaceous ages (140–129 Ma). They show large ion lithophile element enrichment in both the Enriched-MORB and Normal-MORB rare earth element patterns. They are characterized by slightly depleted isotopic compositions, high MgO, Cr, Ni and Mg# values as well as the low SiO2, suggesting a depleted mantle source affinity. The enriched NdHf (εNd(t) = −14.50 to −13.47; εHf(t) = −9.27 to −8.82) and unradiogenic Pb isotopes imply that Jingwan samples originated from a depleted mantle source metasomatized by lower continental crustal materials. Their relatively enriched zircon εHf(t) values (−15.8 to −1.6) and δ18O values (4.82‰–8.77‰) along with their Paleoproterozoic to Neoproterozoic inherited zircons also argue for the contribution of low continental crustal materials from the North China Craton. In contrast, Putaozhuang, Nianpanzhuang, and Niujiaowan samples have positive whole-rock εNd(t) values (4.08–5.20) and εHf(t) values (3.23–5.62). Combined with the existence of Paleozoic zircons, high zircon εHf(t) values, and high Nb/U ratios, these materials suggest that they originated from a depleted mantle source metasomatized by juvenile crust and terrigenous sediments. This is corroborated by variable zircon δ18O values (5.57‰–9.63‰) and mantle-like δ18O values (5.08‰–5.60‰) of Paleozoic inherited zircons from Niujiaowan samples. The distinct geochemical characteristics of Early Cretaceous mafic rocks are induced by the incorporation of different components from subducted crust and sediments into the depleted mantle source. Paleo-Pacific Plate far-field effects controlled the intense lithospheric extension and thinning of the Early Cretaceous MORB-like rocks in the SNCC, which were placed in an immature back-arc basin setting.

Origin of calcite cements in the Permian Lucaogou Formation tight reservoirs, Jimsar sag, Junggar basin, NW China: Constraints from geochemistry

Understanding the diagenetic evolution of carbonate cementation in hydrocarbon reservoirs is critical to better reconstruct the history of fluid flow during petroleum accumulation. The extensive occurrence of carbonate cements within the lower Permian Lucaogou Formation tight reservoirs is regarded as a major diagenetic factor that causes strong hydrocarbon reservoir heterogeneities. Petrographic and geochemical analyses, including optical microscopy fitted with cathodoluminescence, scanning electron microscopy, carbon and oxygen stable isotopes, in situ rare earth element, as well as fluid inclusion microthermometry, were carried out to decipher the origin of calcite cementation and understand its control on reservoirs quality. Petrography shows that the precipitating cements mostly consist of pore-filling blocky/mosaic calcite, with a dull orange luminescence color. Chondrite-normalized rare earth element (REE) patterns and C–O isotopic compositions of these calcite cements exhibit strongly negative Eu and Tb anomalies, enrichment in light REE, positive carbon (δ13CPDB = 0.58‰–7.45‰) and negative oxygen (δ18OPDB = −11.38‰ to −8.61‰) isotopic values, similar to the dolostone and micritized peloidal grains, suggesting that the calcite-precipitating fluids were derived from dissolution of lacustrine depositional carbonates. The relative timing of calcite precipitation in reservoirs was constrained based on the thermal-burial history of the study region and precipitation temperatures obtained from fluid inclusions. The results show that this cementation episode mainly occurred during the Late Triassic to Early Jurassic, which was synchronous with the tectonic uplift event. Moreover, homogenization temperatures of fluid inclusions and geochemical signatures of the calcite cement are similar to those of the fracture-fillings, suggesting that these two calcite phases may be genetically related and form coevally within one fluid flow system. It can be interpreted as a response to the compressional tectonic deformation given by the collision of the Qiangtang Block with the Eurasia Plate. This tectonic deformation event is regarded as the driver for calcite precipitation during the early burial stage, resulting in a considerable reduction of reservoir quality. Calcite cementation is pervasive and may play a main role in halting hydrocarbon migration through some of the permeable pathways in reservoirs.

Geochemical evaluation of the genetic relationship of Kısacık (Ayvacık, Çanakkale/Türkiye) epithermal gold mineralization using trace and rare earth elements

The Kısacık gold deposit is situated in the Biga Peninsula, Northwest Anatolia, Türkiye. The aim of this study is to investigate the genetic relationship between the Kısacık gold deposit and the surrounding rocks using trace element and rare earth element (REE) geochemistry. The results show that the gold mineralizations in the Kısacık area have a compatible pattern with the Alakeçi-Kısacık Volcanics and the Kuşçayırı plutonic rocks in the near vicinity of the area. The gold mineralizations in the Kısacık area are consistent with the trace and rare earth element (REE) patterns of the upper continental and lower continental crust, as shown by comparison with spider diagrams normalized to different geological settings. The gold enrichments in the listvenites and ultramafic rocks in the area are also consistent with the trace and REE element patterns of these rock types. The results of this study support the conclusion that the gold mineralization in the Kısacık area is related to hydrothermal fluids that leached elements from the Alakeçi-Kısacık Volcanics. In addition, hydrothermal fluids from plutonic rocks were also effective in the mineralization process. These results suggest that the gold mineralization in the Kısacık area is related to hydrothermal fluids that leached elements from the Alakeçi-Kısacık Volcanics.

Hammerscale and slag inclusions: New insights into metal supply during the early iron Age in Western Europe

Understanding the nature and origin of iron processed in ancient smithing workshops is essential for unraveling procurement strategies and, more broadly, the circulation of iron. Studying smithing slags traditionally proves complex due to their diverse compositions influenced by hearth substances. Another technique, analyzing slag inclusions in metallic fragments, offers direct insights into the iron's chemical nature. However, the scarcity or absence of these fragments poses challenges in assessing sample representativeness. An alternative approach studies hammerscale, hot iron waste from hammering, providing insights into iron's chemical composition and source. At Weyersheim, an early Iron Age site in France, extensive analysis of 300 hammerscale samples and 77 slag inclusions in 6 iron scraps unveiled a unique geochemical signature. This signature showcases enrichment in Vanadium (V > 800 ppm), Chromium (Cr > 400 ppm), Rare Earth Elements (REE) (∑REE + Y > 1500 ppm), especially Heavy Rare Earth Elements like Yb (>100 ppm), and High Field Strength Elements (HFSE) (e.g., U > 30 ppm). The remarkable chemical uniformity observed in various hammerscale samples, and the slag inclusions indicates that the majority of the processed iron originates from a singular source. Comparison with known iron artifacts, particularly the bi-pyramid iron bars revealed similarities. This source exhibited uncommon enrichment and partitioning patterns of REEs, hinting at a rare geological deposit or a closely associated group of deposits. Plausibly sourced from weathered peralkaline rocks, the iron ore's geological origins potentially link to regions like Vosges and the Black Forest massifs. Nevertheless, identifying the geological formations accountable for these distinctive iron traits remains challenging, as there have been no findings of deposits or iron slag with similar compositions to aid in identification.

Trophic transfer of rare earth elements in the food web of the Loire estuary (France)

The increasing use of rare earth elements (REEs) in many industrial sectors and in medecine, causes discharges into the environment and particularly in estuarine areas subjected to strong anthropogenic pressures. Here, we assessed the distribution of REEs along the food web of the Loire estuary. Several species representative of different trophic levels were sampled: 8 vertebrates, 3 crustaceans, 2 mollusks, 3 annelids and 4 algae, as well as Haploops sp. tubes rather related to sediment. The total REE concentrations measured by ICP-MS were the highest in Haploops sp. tubes (141.1 ± 4.7 μg/g dw), algae (1.5 to 34.5 μg/g dw), mollusks (9.9 to 12.0 μg/g dw), annelids (0.7 to 19.9 μg/g dw) and crustaceans (1.4 to 6.3 μg/g dw) and the lowest in vetebrates (0.1 to 1.6 μg/g dw). The individual contribution of REEs was, however, similar between most studied species with a higher contribution of light REEs (76.7 ± 7.6 %) compared to heavy REEs (14.1 ± 3.7 %) or medium REEs (9.2 ± 5.8 %). Trophic relations were estimated by stable isotope analysis of C and N and the linear regression of δ15N with total REE concentrations highlighted a trophic dilution with a corresponding TMS of −2.0. The tissue-specific bioaccumulation investigated for vertebrates demonstrated a slightly higher REE accumulation in gonads than in the muscle. Finally, positive Eu, Gd, Tb and Lu anomalies were highlighted in the normalized REE patterns of most studied species (especially in fish and crustaceans), which is consistent with results in the dissolved phase for Eu and Gd. These anomalies could either be due to anthropogenic inputs or to various bioaccumulation/elimination processes according to the specific species physiology. This study, including most of the trophic levels of the Loire estuary food web provides new insights on the bioaccumulation and trophic transfer of REEs in natural ecosystems.

Geochemical insights into secular changes in the depositional environment of ferromanganese nodules in the western North Pacific

Understanding Earth's surface dynamics and biological evolution requires deciphering past marine environmental changes. Hydrogenetic ferromanganese nodules formed by the direct precipitation of Fe–Mn oxide/hydroxide from seawater could record the marine environment at the time of deposition, as in the case of ferromanganese crusts. In this study, petrological and geochemical analyses were conducted on ferromanganese nodules collected from the Japanese Exclusive Economic Zone around Minamitorishima Island in the western North Pacific Ocean. Additionally, the results were compared with those of ferromanganese crusts distributed in the same area to elucidate the secular changes in the depositional environment. The mineralogical features (consisting solely of Fe-vernadite with an absence of 10 Å Mn oxide) and the geochemical characteristics (including positive Ce-anomaly and negative Y-anomaly in rare-earth element patterns, high Co contents, and low Cu and Ni contents) of the nodules suggest that the studied nodules are of a hydrogenetic origin. From the inside to the outside of the nodule, the Mn/Fe and Y/Ho ratios decrease while the Th/U ratio increases, indicating a changing depositional environment over time. A similar trend was observed in ferromanganese crusts from the nearby Takuyo-Daigo Seamount. Furthermore, similar compositional changes were observed on the surfaces of the crust samples (uppermost 1–3 mm), which correlated with depth-related changes in seawater oxygen concentrations. Therefore, the observed cross-sectional changes in the chemical compositions of the nodules and crusts may reflect changes in seawater-dissolved oxygen concentrations over time. The Mn/Fe and Y/Ho trends indicate a shift towards a less oxic environment with increasing age while maintaining the current depth profile, implying an expansion of the oxygen minimum zone (OMZ). Moreover, the observed Ni and Cu enrichment, together with the changes in the Mn/Fe and Y/Ho ratios, suggest that the expansion of the OMZ was caused by increased surface ocean productivity.