Light Rare Earth Research Articles

Rare Earth Element Binding and Recovery by a Beta Roll-Forming RTX Domain.

The Block V of the RTX domain of the adenylate cyclase protein from Bordetella pertussis is disordered, and upon binding eight calcium ions, it folds into a beta roll domain with a C-terminal capping group. Due to their similar ionic radii and coordination geometries, trivalent lanthanide ions have been used to probe and identify calcium-binding sites in many proteins. Here, we report using a FRET-based assay that the RTX domain can bind rare earth elements (REEs) with higher affinities than calcium. The apparent disassociation constants for lanthanide ions ranged from 20 to 75 μM, which are an order of magnitude higher than the affinity for calcium, with a higher selectivity toward heavy REEs over light REEs. Most proteins release bound ions at mildly acidic conditions (pH 5-6), and the high affinity REE-binding lanmodulin protein can bind 3-4 REE ions at pH as low as ∼2.5. Circular dichroism (CD) spectra of the RTX domain demonstrate pH-induced folding of the beta roll domain in the absence of ions, indicating that protonation of key amino acids enables structure formation in low pH solutions. The beta roll domain coordinates up to four ions in extreme pH conditions (pH < 1), as determined by equilibrium ultrafiltration experiments. Finally, to demonstrate a potential application of the RTX domain, REE ions (Nd3+ and Dy3+) were recovered from other non-REEs (Fe2+ and Co2+) in a NdFeB magnet simulant solution (at pH 6).

A synergistic solution for fighting fraudulent practices in squid using light stable isotope ratios and lanthanide tracers

To identify a novel optimized strategy for preventing fraudulent substitutions of squid species and origins, forty European squids (Loligo vulgaris) and forty flying squids (Todarodes sagittatus) from the Mediterranean Sea and Atlantic Ocean were analyzed for δ13C, δ15N, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu using isotope ratio mass spectrometry and inductively coupled plasma-mass spectrometry. While δ13C and δ15N variations were mainly species-related, they alone could not reliably distinguish samples. To address this issue, decision rules were developed using Classification and Regression Tree analysis. Threshold values for δ13C (−19.91‰), δ15N (14.87‰), and Pr (0.49 μg kg−1) enabled successful discrimination among Mediterranean European squids, Atlantic European squids, Mediterranean flying squids, and Atlantic flying squids, achieving over 90% accuracy, 81% precision, 80% sensitivity, and 93% specificity. This method holds promise for enhancing traceability and safety in the seafood industry, ensuring product integrity and consumer trust.

Rare earth mineralization in ores of the Gurvunur apatite-magnetite deposit (Ozerny ore cluster, Western Transbaikalia)

The Gurvunur apatite-magnetite deposit is located within the Ozerny ore cluster in Wes-tern Transbaikalia. A peculiarity of this object is the presence of rare-earth mineralization in the ores. The main REE concentrator minerals include monazite, allanite, apatite, and epidote. One of the main concentrators of REE is apatite, where the content of REE sum reaches 2.6 wt. %. The REE are mainly represented by light lanthanides, with La up to 1.8 wt. % and Ce up to 2.08 wt. % predominating. Monazite- (Ce) is formed in the process of apatite refining, leading to the monazite fine-grained dissemination and veinlets occurring. Epidote is found in nests and vein-like formations of skarn aggregates. The mineral mainly contains light lanthanides (La up to 5.11 wt. %, Ce up to 2.47 wt. %) and forms gradual transitions to allanite that, in its turn, is also found in the form of isolated segregations or as a part of aggregates of epidote-allanite composition. Light lanthanides with Ce up to 14.35 wt. % and La up to 9.16 wt. % pre-dominate in the allanite composition. The study of the mineral composition and distribution of REE in ores and minerals allows us to conclude that rare-earth mineralization in the ores of the Gurvunur apatite-magnetite deposit was formed as a result of skarning of the carbonate-bearing volcanogenic-sedimentary rocks, and the source of rare-earth mineralization was granodiorites of the Vitimkan intrusive suite.

Characterization of Rare Earth Elements in Cassiterite-Associated Minerals in Bangka-Belitung Islands, Indonesia

Rare earth elements (REEs) are crucial to numerous industries of high-technology as raw materials. The growth of a long-term relationship between REE supply and demand to develop hi-tech industries is becoming tight in the world market, while the mineral supply chain is being distorted by COVID-19. The availability of information and data regarding the REE resource potential and characteristics are interesting research subjects to examine its economic value as alternative sources. This research aims to provide basic information about the existence and characteristics of REEs in cassiterite-associated minerals located in Bangka and Belitung Islands. Fifty-one samples consisting of primary deposits, placer deposits, concentrates, and tailings were collected from the southern Bangka and Belitung region. The samples were analyzed using microscope, x-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe micro-analysis (EPMA), and inductively coupled plasma mass spectrometry (ICP-MS). The results show that the REE-bearing minerals comprised monazite and xenotime. Monazite, the most dominant REE-bearing mineral, contains light REEs (Ce-dominant), while xenotime contains heavy REE (Y-dominant). The results of SEM with energy-dispersive spectroscopy show that monazite contains other LREE (La and Nd), and xenotime also contains other HREE (Dy and Yb). Moreover, zircon and ilmenite can be considered as economical cassiterite-associated minerals that have other mineral inclusion, but have no REE contain.

How do seasonal, significant events, and policies affect China's REE export prices? Based on deep learning perspective

This paper aims to accurately predict China's rare earth export prices and reveal the impact of variables such as seasonality, significant events, finance, and supply and demand on rare earth price volatility. Daily datasets of light and heavy rare earths from 2011 to 2023 were used, and the Tree-structured Parzen Estimator-Temporal Fusion Transformer model was employed to predict rare earth prices. Complete Ensemble Empirical Mode Decomposition with Adaptive Noise and partial dependence plots were used to reveal the factors affecting price volatility. The following conclusions were drawn: (1) The Tree-structured Parzen Estimator-Temporal Fusion Transformer deep learning model can provide more accurate rare earth price prediction information; (2) Light rare earth prices are more susceptible to cyclical influences, while heavy rare earth prices are more affected by significant events. The outbreak of COVID-19 has had a long-term impact on both light and heavy rare earth prices; (3) The fluctuations in heavy rare earth prices are mainly influenced by financial factors, while the fluctuations in light rare earth prices are influenced by multiple factors such as finance, supply and demand, and macroeconomics; (4) An increase in resource tax rates may lead to a decrease in rare earth prices, while an increase in restrictions on rare earth mining may lead to an increase in rare earth prices.

Arc building and maturation of the Lombok Island, East Sunda Arc

Intra-oceanic subduction zones are major sites of crust–mantle material exchange and crustal growth; however, the processes responsible for the magmatic evolution and transformation of nascent arcs into mature oceanic arcs with thicker crust are debated. We present mineral chemistry, zircon UPb age and Hf isotopic data, and whole-rock chemical and Sr–Nd–Hf–Pb isotopic data for Cenozoic volcanic rocks on Lombok in the East Sunda Arc, Indonesia, to investigate their petrogenesis and arc maturation. SIMS zircon UPb analyses of lavas from southern Lombok yield an early Oligocene age of ∼30 Ma. The lavas can be divided into three groups based on their ages and geochemical characteristics: group I (late Eocene) and II (∼30 Ma) lavas from southern Lombok, and group III lavas (∼3–0 Ma) from northern Lombok. The lavas are characterized by a progressive enrichment in K2O and incompatible element contents, and NdHf isotopic compositions with time. Group I lavas are tholeiitic basalts with low K2O contents (0.15–0.17 wt%) and Indian-MORB like rare earth element (REE) patterns and NdHf isotopic compositions (εNd = +7.4; εHf = +14.5), enrichment in large-ion lithophile elements (e.g., Rb, U, and K), and typical forearc basalt (FAB) geochemical characteristics. Group II lavas are low-K basaltic andesites to dacites that yield flat chondrite-normalized REE patterns [(La/Sm)N = 0.9–1.4], uniform initial 87Sr/86Sr ratios (0.7038–0.7042), and positive εNd(t) (+5.9 to +6.8) and εHf(t) (+13.9 to +14.4) values. Group III lavas are typically medium- to high-K calc-alkaline basalt to andesite and are enriched in light REEs [(La/Sm)N = 1.6–3.3] with uniform initial 87Sr/86Sr ratios (0.7038–0.7042) and slightly low εNd(t) (+3.9 to +5.4) and εHf(t) (+10.5 to +12.5) values. Progressive enrichment in incompatible element contents and NdHf isotopic compositions over time, from FAB to high-K calc-alkaline lavas, reflect the maturation of the East Sunda Arc. Sr–Nd–Pb–Hf isotopic mixing models, along with trace element ratios (e.g., Ba/Th, La/Yb, Th/Yb), suggest that increasing amounts of sediments were incorporated into the mantle sources of the magmas from group I (∼0%) to group II (<0.5%) and group III (0.5%–1.0%) lavas. Partial melting models show that the formation of group I and II lavas can be reproduced by high-degree (∼10%) partial melting of spinel peridotite, whereas the group III lavas were formed by low-degree (∼5%) partial melting of spinel peridotite. We propose that the evolution of Lombok arc magmas was controlled mainly by the fluxes of subducted slab material, along with decreasing degrees of partial melting as a result of crustal thickening over time.

Indigenous microbial influence on REE enrichment and fractionation in South China weathering crusts: Insights from experimental simulations

The activity of microorganism plays an important role on the enrichment, migration and fractionation of rare earth elements (REEs) in the supergene environment. To investigate the characteristics of indigenous microorganisms on the enrichment and fractionation of REEs, we studied the adsorption efficiencies of REEs by 30 indigenous microbial strains that were isolated and cultured from the weathering profile of a regolith-hosted REE deposit in South China. Most microbial strains exhibited high adsorption efficiencies for REEs, ranging from 2.3 to 42.9 mg g−1. Notably, the taxonomic classification of microorganisms significantly influenced the adsorption selectivity. Gram-positive bacteria exhibited a pronounced enrichment of the heavy REEs, while gram-negative bacteria showed no obvious adsorption preference. The tetrad effects were observed in REE adsorption patterns of gram-negative bacteria and fungi; however, fungi demonstrated a much higher affinity for light and medium REEs. Chemically modified microbial cells were employed to investigate the adsorption mechanism, revealing that distinct functional groups of microbial cells corresponded to the adsorption preference of microorganisms towards REE. Carboxyl and phosphate groups contributed to a relatively high adsorption capacity for light REEs and heavy REEs, respectively. The findings of our study suggest that the distinct composition of microbial groups may exert a significant influence on the biogeochemical cycle of REE in weathering profiles.

Identification of the EMII-type mantle end-member of the Kerguelen mantle plume and its implications for the initial breakup of eastern Gondwana: New constraints from the Cretaceous diabase in the Tethyan Himalaya

The breakup of eastern Gondwana during the Early Cretaceous has been well-documented. However, the relationship between Cretaceous mafic magma and the Kerguelen mantle plume has not been well-constrained. It is also unknown if the Kerguelen mantle plume in the Tethyan Himalaya played a key role in triggering the breakup of eastern Gondwana. The petrogenesis and geodynamic processes of the coeval magmatism in the Tethyan Himalaya might provide value insights into this issue. In this study, we conducted petrological, geochronological, and geochemical investigations on a recently identified diabase from the Yamdrok Lake. The diabase contains zircon grains with a U-Pb age of 138 ± 8 Ma, suggesting the emplacement at the Early Cretaceous. Geochemically, the studied samples display OIB-like trace elemental features that are enriched in light rare earth elements (LREEs) but no significant depletion in high field strength elements (HFSEs), such as Nb, Ta, and Ti. Furthermore, they have relatively uniform Sr-Nd-Pb-Hf-O isotopic compositions with initial 87Sr/86Sr ratios varying from 0.70563 to 0.70623, εNd(t) and εHf(t) values range from 0.6 to 0.8 and 1.0–2.4, respectively, whole-rock δ18O values of 6.42 ‰ to 7.50 ‰, and (208Pb/204Pb)i = 38.995 ∼ 39.285, (207Pb/204Pb)i = 15.673 ∼ 15.698, and (206Pb/204Pb)i = 18.689 ∼ 18.914, similar to an EMII-type enriched mantle. And recycled shallow continental crustal materials into the OIB-like mantle source might account for the EMII-type mantle features observed in this study. Considering the Kerguelen mantle plume locating beneath the triple junction of Australia, Antarctica, and Greater India, we propose that the mafic rocks in this study might be genetically related to the early activity or even initiation of the Kerguelen plume during the Early Cretaceous. Our study further indicates that the Kerguelen mantle plume contains EMI- and EMII-type isotopic compositions, which are characterized by geochemical complexity and variation.

Quantifying the Criteria Used to Identify Zircons from Ore-Bearing and Barren Systems in Porphyry Copper Exploration

Abstract Zircon is a common mineral in igneous rocks, which is resistant to both chemical weathering and physical abrasion. Its chemistry can potentially be used to distinguish ore-forming porphyry magmas from barren magma systems. This study compiles &amp;gt;23,000 zircon analyses from &amp;gt;30 porphyry deposits, barren intrusions, and rivers to determine the principal geochemical characteristics of fertile zircons using predictive modeling, and compares them with traditional geochemical thresholds. The results show that the Eu/Eu* and Dy/Yb ratios, P content, and the curvature at the end of rare earth element (REE) patterns (λ3) are the most diagnostic characteristics of fertile zircons. The use of geochemical thresholds, as Boolean conditions, reach their maximum performance for Eu/Eu* and Dy/Yb (sensitivity [sens] = 0.73, specificity [spec] = 0.90), but it is outperformed by the random forest model (sens = 0.91, spec = 0.93) in the testing set. Explanatory analysis of the models shows that the fertility signal in zircons becomes stronger as the porphyry system evolves and is accompanied by an overall decrease in the middle to light REE and P content, characteristics that are absent in barren zircons. We attribute the observed difference in λ3 to the co-crystallization of other accessory phases, suggesting that the changes in the zircon Ce anomaly is controlled by the depletion of light and middle REE. The low P content in fertile zircons is caused by extensive crystallization of apatite. Fertile zircons have an excess of (REE + Y)3+, which we attribute to charge-balance by H+ in hydrous magmas. Simple machine learning algorithms outperform the traditional geochemical discriminators in their predictions and provide insights into characteristics that have not previously been considered for evaluating porphyry copper fertility using zircon geochemistry. We propose simplified methods that can be easily incorporated into exploration workflows.

Rare earth elements redistribution in mine tailings soil: A comparative study of sunlit and shady slopes after in-situ leaching

The in-situ leaching of rare earth minerals results in ecological differences between sunlit and shady slopes, which may be related to differences in the distribution REEs in the associated soil matrices. Studies of REEs mine tailings in Southern China indicated higher total concentrations of REEs on sunlit slopes compared to shady ones. Specifically, the exchangeable REEs fraction (F1-REEs) was higher on the shady slopes, whereas the Fe/Mn oxides bound REEs fraction (F3-REEs) was higher on the sunlit slopes. In addition, light REE (LREE) concentrations were lower at lower elevations. With the exception of the Ce fraction which remained stable, this indicated a change in all REEs distributions, moving from F1-REEs towards the residual fraction. Hierarchical cluster and principal component analysis revealed a strong correlation between F3-REEs, organic matter bound REEs (F4-REEs), and LREEs, and a positive association of F3-REEs with sunlight exposure. Partial Least Squares Path Modeling analysis suggested that OM promoted the conversion of LREEs to F3 and F4-REEs in soil driven by sunlight exposure. Additionally, as the Feo/Fed ratio decreased, more LREEs were converted to F3. This study suggests that sunlight and elevation both play a critical role in the geochemical dynamics of REEs in in-situ tailings, advocating for environmental evaluations to be undertaken in order to accurately understand the ecological impacts of rare earth mining.

Extreme geochemical fractionation during mantle melting: Insights from Hf-Nd isotopically ultra-depleted eclogite

Extreme fractionation of elements and isotopes in mafic igneous rocks is abnormal in deciphering the source nature and melting conditions of mafic magmatism. Especially, identification of geochemically ultra-depleted mafic melts and their mantle sources has great bearing on the property of crust-mantle differentiation at plate margins. This is illustrated by extreme Hf-Nd isotope fractionation in ultrahigh-pressure eclogites from the Sulu orogen in east-central China. In addition to the previous finding of ultrahigh εNd(0) values, we report here new data of whole-rock trace elements and Lu-Hf isotopes in eclogites and related rocks from the same region. The present results show extremely high Lu/Hf ratios and abnormally high εHf(0) values of up to 576 for the eclogites, significantly different from the garnet amphibolites and other eclogite-facies metamorphic rocks in the same orogen. This feature is coupled with the ultrahigh εNd(0) values as well as the severe depletion of light rare earth elements (LREE) and high field strength elements (HFSE). Because HFSE and LREE are immobile in aqueous solutions and the effect of melt extraction is insignificant during the continental deep subduction, the extreme fractionation of Lu/Hf and Sm/Nd indicate their origination from a geochemically ultra-depleted mantle source. These eclogites have the depleted mantle Hf model ages of 1.27 Ga to 1.61 Ga, similar to the depleted mantle Nd model ages of 1.39 Ga to 1.67 Ga as previously reported. This suggests that the protolith of the extremely high εHf-εNd eclogites was a kind of mafic igneous rocks derived from fractional crystallization of geochemically ultra-depleted mafic melts, which were produced by partial melting of the highly refractory lithospheric mantle during a series of seafloor spreading initiation-failure cycles at a divergent plate margin after the breakup of supercontinent Columbia in the Early Mesoproterozoic. The mafic igneous rocks were located in a passive continental margin in the Late Paleozoic and experienced deep subduction and exhumation in the Triassic, giving rise to the presently studied eclogites. The ancient geochemical signatures were retained without considerable influence by mantle convection, providing insights into the nature of crust-mantle differentiation during the tectonic transition from supercontinental breakup to seafloor spreading beneath the sub-ridge lithospheric mantle.

Fate and potential ecological risk of rare earth elements in 3000-year reclaimed soil chronosequences

The introduction of anthropogenic inputs into natural systems may lead to enduring alterations in the innate characteristics of Rare Earth Elements (REEs). Against this backdrop, the evolutionary processes and environmental drivers of REEs in soil remain uncertain. A 3000-year soil chronosequence with uniform parent material was established in reclaimed farmland along the Yangtze River, reconstructing, for the first time, the dynamic processes of REE accumulation and fractionation over a long-time scale. Analysis of 122 soil samples showed REE concentrations ranging from 146.00 to 216.56 μg/g. Based on reclamation duration, three significant stages of REE evolution were identified: natural leaching, rapid accumulation, and stable accumulation with differentiation. Reclaimed soil after 3000 years exhibited a 14.1 % increase in REE concentrations compared to fresh sediments, attributed to anthro -pedogenic processes. Moreover, Heavy Rare Earth Elements (HREEs) accumulated faster than Light Rare Earth Elements (LREEs), particularly in deeper soils (60–100 cm), where HREE concentrations rose by 34.3 %, mainly due to acidic environments promoting HREE fixation. Additionally, the potential ecological risk posed by REEs heightened with reclamation duration, with HREEs exhibiting a sensitivity of 83 % to 94 %. Our findings stress the urgency of carefully monitoring exogenous REEs introduced through anthropogenic activities, particularly HREEs.

Geochronology, geochemistry, and isotope signatures of porphyries from the dabate Mo—Cu deposit, Western Tianshan, China: Implications for petrogenesis and geodynamic setting

The Dabate deposit in the West Tianshan Orogenic Belt is a large porphyry Mo-Cu deposit with obvious zoning feature. The Dabate pluton is closely related to mineralization associated with the rhyolite and granite porphyries. Copper (Cu) mineralization occurs on the margin of the rhyolite porphyry, and molybdenum (Mo) mineralization occurs in the interior of the rhyolite porphyry. Petrology, zircon U-Pb isotopic data, whole-rock geochemistry, and Sr-Nb-Hf-Pb isotopic data of the rhyolite and granite porphyries in the Dabate Mo-Cu mining zone and to discuss the properties, sources, evolution, and tectonic environment of the magma. Zircon U-Pb age dating shows that the rhyolite porphyry and granite porphyry were formed in 300.1 ± 1.3 Ma and 290.4 ± 5.2 Ma, respectively, and they are geochemically similar. Both are characterized by negative Eu anomalies (δEu = 0.09–0.15 and 0.10–0.11, respectively) and are slightly rich in light rare earth elements (LREE) but depleted in high-field-strength elements (HFSE), which indicates that they are both A2 type granites that underwent high differentiation. The Sr isotope (ISr) values for the rhyolite and granite porphyries range from 0.70564 to 0.70658 and 0.70833–0.70954, respectively. The Nd isotopic composition [εNd(t)] values for both are negative but close to zero (−0.25 to −0.46 and −0.65 to −1.10, respectively), and the two-stage depleted mantle Nd model ages (TDM2(Nd)) are 1.07–1.10 Ga and 1.11–1.14 Ga, respectively. Zircon εHf(t) values are 7.29–11.97 and 6.26–11.08 for rhyolite porphyry and granite porphyry, respectively, and the two-stage Hf model ages (TDM2(Hf)) are 550–848 Ma and 605–916 Ma, respectively. The initial Pb isotope ratios for the rhyolite and granite porphyry are close at (206Pb/204Pb)i = 18.26–18.65, (207Pb/204Pb)i = 15.54–15.64, and (208Pb/204Pb)i = 38.19–38.57. These results indicate that the two porphyries have a mixed source, likely originating from the partial melting of mantle blended with some recently formed lower crust material. The geochronology, geochemistry, and Sr-Nd-Hf-Pb isotope data of existing intrusions in the West Tianshan imply that the Late Carboniferous to Early Permian Dabate area was underplated in a post-collisional extensional setting, and A2-type granite intrusions with related Mo-Cu mineralization were formed.

Mineralogical Characteristics of Color-Changing Garnet and the Effect of Light Path Length on Color

The color-changing garnet displays the “alexandrite effect”, changing from green in daylight to purplish-red under incandescent light. The mineralogical characteristics of color-changing garnet is analyzed using Raman spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, an electron probe, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The color of garnets with different thicknesses was calculated using the International Commission on Illumination (CIE 1976) L*a*b* uniform color system. The results revealed the presence of rutile inclusions in color-changing garnet. Strong absorption in both the blue-violet zone and orange-yellow zone was the main cause for the color-changing effect of garnet. The distribution pattern of rare earth elements (REE) was left-leaning, showing the enrichment of heavy rare earth elements (HREE) and depletion of light rare earth elements (LREE). As the total Cr and V concentrations increased, the area of the 574 nm absorption peak in the UV-Vis spectrum also increased, leading to a more significant variation in color ΔE*ab. The light path length of the gemstone had a significant impact on the extent of the color-changing effect. The color difference reached a maximum and the color-changing effect was most visible when the thickness of the gemstone was 5 mm.

Sodium alginate/polyvinyl alcohol for the recovery of rare earth elements from mining wastewater: Mechanism and properties

With the demand for rare earth elements (REEs) increasing in the high-tech sector, the recovery of REEs from secondary sources is becoming very critical. In this study, sodium alginate/polyvinyl alcohol (SA/PVA) beads obtained by cross-linking alginate with polyvinyl alcohol were used to recover REEs from real rare-earth wastewaters. The results showed that SA/PVA beads are less affected by temperature and exhibited adsorption selectivity for REEs. The efficiency of adsorbing REEs ranged from 27.6% to 52.6%, but was significantly higher than that of 9.2% Mn. Meanwhile, among the observed REEs, SA/PVA beads revealed a preference for light REEs (44.3% − 52.6%). The adsorption process was investigated utilizing advanced characterization methods, namely Scanning Electron Microscope, Fourier Transform Infrared Spectrometer, and X-ray Diffraction Spectra. Combined with the results of Pearson correlation analysis, we proposed that the adsorption process involves the combined effects of ion exchange, complexation, electrostatic interaction and pore filling. As well, a desorption efficiency of more than 76.9% can be achieved with sodium citrate, which makes possible the effective recovery of REEs. In summary, this study provides a promising green, environmentally friendly and sustainable material for the enrichment and recovery of REEs from mining wastewater.

Lateral redox variability in ca. 1.9 Ga marine environments indicated by organic carbon and nitrogen isotope compositions.

The stepwise oxygenation of Earth's surficial environment is thought to have shaped the evolutionary history of life. Microfossil records and molecular clocks suggest eukaryotes appeared during the Paleoproterozoic, perhaps shortly after the Great Oxidation Episode at ca. 2.43 Ga. The mildly oxygenated atmosphere and surface oceans likely contributed to the early evolution of eukaryotes. However, the principal trigger for the eukaryote appearance and a potential factor for their delayed expansion (i.e., intermediate ocean redox conditions until the Neoproterozoic) remain poorly understood, largely owing to a lack of constraints on marine and terrestrial nutrient cycling. Here, we analyzed redox-sensitive element contents and organic carbon and nitrogen isotope compositions of relatively low metamorphic-grade (greenschist facies) black shales preserved in the Flin Flon Belt of central Canada to examine open-marine redox conditions and biological activity around the ca. 1.9 Ga Flin Flon oceanic island arc. The black shale samples were collected from the Reed Lake area in the eastern part of the Flin Flon Belt, and the depositional site was likely distal from the Archean cratons. The black shales have low Al/Ti ratios and are slightly depleted in light rare-earth elements relative to the post-Archean average shale, which is consistent with a limited contribution from felsic igneous rocks in Archean upper continental crust. Redox conditions have likely varied between suboxic and euxinic at the depositional site of the studied section, as suggested by variable U/Al and Mo/Al ratios. Organic carbon and nitrogen isotope compositions of the black shales are approximately -23‰ and +13.7‰, respectively, and these values are systematically higher than those of broadly coeval continental margin deposits (approximately -30‰ for δ13Corg and +5‰ for δ15Nbulk). These elevated values are indicative of high productivity that led to enhanced denitrification (i.e., a high denitrification rate relative to nitrogen influx at the depositional site). Similar geochemical patterns have also been observed in the modern Peruvian oxygen minimum zone where dissolved nitrogen compounds are actively lost from the reservoir via denitrification and anammox, but the large nitrate reservoir of the deep ocean prevents exhaustion of the surface nitrate pool. Nitrogen must have been widely bioavailable in the ca. 1.9 Ga oceans, and its supply to upwelling zones must have supported habitable environments for eukaryotes, even in the middle of oceans around island arcs.

Geochemical and Isotopic Constraints on the Origin of Rare-Metal Enriched Alkaline A-Type Granites from the Nubian Shield: Role of Mantle Metasomatism

Abstract The U-Pb zircon TIMS age of 637.47 ± 0.23 Ma identifies the oldest anorogenic complex in the northern Nubian Shield as that at Mount Hamr, emplaced as elongated plutons along deep-seated faults, intruding the Pan-African shield rocks. The hypersolvus peralkaline granites of Mount Hamr are dominated by perthite, quartz, and arfvedsonite, along with accessory zircon, chevkinite-(Ce), monazite, aenigmatite, apatite, fluorite, and opaque ilmenite. The rocks are depleted in Al, Ca, and Sr and enriched in Rb, high field strength elements (Zr, 528–1115 ppm), and rare earth elements (ΣREE, 416–1648 ppm), showing fractionated, light rare earth element-enriched patterns [(La/Yb)N = 17]. The rocks are classified as ferroan, reduced A-type granites (A1-subtype) and exhibit age-corrected (143Nd/144Nd)(i) ratios ranging from 0.5115 to 0.5117, with [ϵNd(t) = +5.0 to +5.9] similar to HIMU-OIB, and have lower age-corrected (87Sr/86Sr)(i) ratios (avg. Sr(i) = 0.702). The data yield Nd-TDM2 model ages of 860–929 Ma. High Zr/Hf, (Ce/Pb)N and low Y/Nb, (Th/Nb)N in these rocks reflect OIB-geochemical-signatures. The rocks crystallized at high temperature (TZr = 900–1185 °C) from H2O–depleted melt via extensive low-pressure fractionation of OIB-type parent magma, initially developed from a Na-F-rich metasomatized mantle source. The latter may have led to the formation of similar rare-metal-enriched alkaline intrusions within the vast Arabian-Nubian Shield and possibly within some magmatic provinces occurring in other shields.

Synthesis, spectroscopic characterization and biological activities of complexes of light lanthanide ions with 3-hydroxyflavone

New solid compounds of light lanthanide ions with 3-hydroxyflavone were synthesized in good yields (up to 85 %). The resulting complexes have been thoroughly characterized using various analytical and spectral techniques, including elemental analysis, complexometry, thermogravimetry, UV–VIS, FT-IR, 1H NMR, 109AgNPET LDI MS and fluorescence spectroscopy. The molecular formulas of the complexes were determined as follows: Ln(3HF)3, where 3HF-3-hydroxyflavone, Ln = La(III), Pr(III), Nd(III) and Ln(3HF)3·nH2O, where n = 1 for Ln = Ce(III), Sm(III), Eu(III), and n = 2 for Gd(III). Thermogravimetric studies revealed that the water molecules in the hydrated compounds are located in the outer coordination sphere. Based on the spectral data, it was noted that lanthanide ions interacted with the 3OH and 4CO groups of 3-hydroxyflavone. The effect of lanthanide ion chelation on the excited-state intramolecular proton transfer (ESIPT) process and fluorescence emission of 3HF was investigated. It was found that coordination with metal ions can suppress the ESIPT process and enhance the fluorescence emission of 3HF. The synthesized compounds were also screened for their antibacterial activity, free radical scavenging capacity, and interaction with BSA. The results showed that the complexes exhibit higher biological activity compared to the ligand.

Evaluation of garnet phenocrysts in volcanic rocks (Görece/İzmir – Western Türkiye) for their usability as a semi-precious gemstone by multi-analytical methods

Garnets are observed as phenocrysts in blocky rhyolites of Cumaovası Volcanites and are reddish-blackish in color, show vitreous luster, and have dodecahedron forms varying between 0.5 and 2.0 cm in size. In optical microscope investigations, they exhibit fractured structures and contain quartz, hematite, chlorite, and acicular rutile inclusions. Garnet phenocrysts are highly consistent with spessartine-type garnet end members in the Raman spectrum. This result is supported by the mineral chemistry results determined as spessartine (Sps)0.50–0.52 almandine (Alm)0.47–0.48 grossular (Grs)0.01–0.02. In the chondrite, primitive mantle, and Mid-Oceanic Ridge Basalt normalized multi element variation diagrams, garnet phenocrysts show enrichment in all elements (except Sr, K, P, and Ti). In contrast, in the upper continental crust normalized multi element variation diagram, garnet phenocrysts show depletion in large ion lithophile elements (Rb, Ba, K, and Sr) relative to high field strength elements. They exhibit slight enrichment in light rare earth elements ((La/Sm)N = 0.11–1.07) relative to heavy rare earth elements ((Sm/Yb)N=0.78–0.97). Furthermore, garnet phenocrysts have significant negative europium (Eu) ((Eu/Eu*)N = 0.01–0.02) and mildly positive cerium ((Ce/Ce*)N = 2.43–13.77) anomalies indicating hot and reduced magma conditions. The Y/Ho ratios have ranged from 18.9 to 20.3 and are close to the chondrite value. The zircon saturation temperatures (TZr) of the garnet’s host rock was determined to be 756 °C. As a result of mineralogical, geochemical and gemological studies, it was concluded that Görece garnet phenocrysts have glassy luster and semi-transparent dodecahedral crystal shapes, so they can be classified as semi-precious gemstones. In addition, the rare earth element content of the garnet phenocrysts is similar to that of industrial garnet sands and it is thought that they may have potential.

Paleoclimatic and environmental conditions of the Lower-Middle Ordovician carbonate reservoir in the middle of Tarim Basin (NW China): Constrained by petrographic, geochemical, and carbon–oxygen isotopic characteristics

Breakthroughs have been made recently in the exploration of hydrocarbon in the middle of Tarim Basin, NW China. The complexity of the Lower-Middle Ordovician carbonate reservoir remains enigmatic and hinders the source, developmental mechanism of the calcite fills, and paleo-environmental conditions of the Yingshan and Yijianfang Formations have been unclear. Here we present the related paleoenvironmental settings and diagenetic history, using petrographic, geochemical, and carbon (13C) and oxygen (18O) isotopic characteristics of calcite fracture, cave, and fissure fillings of a Lower-Middle Ordovician carbonate reservoir. The results indicate that the limestone caves dominantly consist of CaO, FeO, and MgO, and minor quantities of TiO2 and MnO. Among the trace elements, Ni reported the highest values (with an average of 1162.16 ppm) and other trace elements such as Ba, V, and Ga occur in minor values (with an average of 71.03, 19.18, and 12.92 ppm) respectively. The enrichment of light rare earth elements (LREEs) over the heavy rare earth elements (HREEs), with positive and negative Ce, and negative Eu anomalies indicate the contexts of oxic and anoxic conditions in seawater and sediments interface. The variation in δ18OPDB values ranges from −4.72 to −14.48‰ (with an average of −10.12‰), indicating a setting of paleo-karstification by atmospheric freshwater dissolution. While the variation in δ13CPDB indicates relatively significant values, ranging between 0.82 to −3.80‰ (with an average of −1.07‰), suggests that the paleo-karstification in this region has experienced episodes of supergene and burial diagenesis. The paleo-temperature average value of 59.1 °C, and the paleo-salinity average (Z-value) of 120.07, indicating a relatively warm paleoclimatic environment during the development of calcite-filling deposits. The results suggest several paleo-environmental conditions when paleokarst occurred: a marine deposition environment, an atmospheric freshwater karstification environment, a shallow burial paleo-karstification environment, and a high-temperature deep-burial environment in Yingshan and Yijianfang Formation in the Shunbei area. This study serves as an analog for similar carbonate systems worldwide, providing valuable insights for understanding paleo-karstification processes in different tectonic and climatic settings. Comparative studies between the Shunbei area, Tarim Basin, and other carbonate platforms contribute to our knowledge of karst evolution and its implications for reservoir development and groundwater resources.