Analysis Of Rare Earth Elements Research Articles

Response of Paleogene Fine-Grained Clastic Rock Deposits in the South Qiangtang Basin to Environments and Thermal Events on the Qinghai-Tibet Plateau.

The Chamdo Basin is a secondary basin in the eastern part of Tibet China and is one of the most promising of petroliferous basins for new petroleum exploration. The Qamdo Basin records a complex burial history from the Mesozoic to the Cenozoic; however, the poorly constrained sedimentology of Cenozoic strata in this basin has severely obscured the overall profile and impeded further explorations of oil and gas resources. Here, we conduct whole-rock geochemical analyses of major, trace, and rare earth elements in fine-grained clastic rocks of the Paleocene Gongjue Formation, Qamdo Basin to reveal depositional environments, provenance, and tectonic setting. Petrologically, the Gongjue Formation is dominated by red fine-grained sandy mudstones/siltstones with ripple marks. The high values of the chemical index of alteration (avg. of 78.93), chemical index of weathering (avg. of 90.10), and index of compositional variability (avg. of 2.5) suggest that the basin has undergone heavy weathering. Cross-plots of La vs Th, Th vs Sc vs Zr/10, and Th vs Co vs Zr/10 reveal a continental arc tectonic setting. Paleosalinity (Sr/Ba), paleoclimate (Sr/Cu), and redox proxies (V/Cr, U/Th, and enrichment factors of Mo and U) indicate brackish to saline and oxidizing paleowater masses during deposition of the Gongjue Formation. Provenance analyses via elements and petrology reveal that sediments in the Gongjue Formation are mainly derived from intermediate-acidic rocks of the upper crust. We conclude that the first and third members are more arid climate and heavily chemically weathered than the second member. In combination with previous studies of the structural evolution of the Qamdo Basin since the Paleogene, a model is built to describe the sedimentary environment and evolution of the Qamdo Basin during transition to the Paleocene. The first and third members, i.e., the Eg1 and Eg3 members of the Gongjue Formation, are dominated by an oxidizing environment of seawater-saltwater, and the climate ranges from warm and humid to arid and hot, with relatively stable environmental changes. The Eg2 member of the Gongjue Formation is dominated by an oxidizing environment of seawater-saltwater, and the climate ranges from warm and humid to arid and hot, with more frequent environmental evolution. Our model aids in better understanding of the Paleocene climate evolution of the eastern Tibetan Plateau.

Was cratonic Asia deeply subducted beneath the Pamir? Evidence from P–T conditions and tectonic affinities of Cenozoic Pamir crustal xenoliths

AbstractOne of the most striking geological features of the Pamir is the south‐dipping lithospheric slab beneath the orogen characterized by an intracontinental Wadati‐Benioff zone. A widely accepted hypothesis over the past 40 years interprets the slab to represent southward subducted cratonic Asian continental lithosphere, which predicts significant cratonic Asia‐sourced crustal materials (e.g., Tarim Basin) beneath the Pamir. Alternatively, recent studies have interpreted the slab to be lithosphere delaminated from the base of the Pamir. To test these hypotheses, depth–tectonic affinity relations of crustal xenoliths carried by Miocene volcanic rocks in the eastern Pamir, interpreted to be sourced from the Pamir deep lithosphere, are used to determine whether they represented Asian affinity cratonic crust. Thermodynamic calculations, zircon U–Pb geochronology combined with rare earth element analysis, and whole‐rock major‐trace element and Sr–Nd isotopic analyses document that (1) eclogite and pyroxenite xenoliths (~31–43 kbar/~960–1170°C) are the deepest sourced portions of the lithosphere from ~100 to 140 km depth, the protoliths of which represent the mid‐lower crustal rocks of the Cretaceous Pamir magmatic arc, rather than material from cratonic Asia, and (2) granulite xenoliths (~20 kbar/~900°C) represent the Cenozoic lower crustal rocks of Pamir terranes from ~70 km depth. These results indicate the south‐dipping slab represents delaminated Pamir lower crust and mantle lithosphere, rather than intracontinental subduction of Asian lithosphere, and further support the hypothesis of minimal Cenozoic northward translation of the Pamir.

Rare-earth element comparative analysis in chosen geological samples using nuclear-related analytical techniques

In this study, four analytical techniques for the detection of Sc, La, Ce, Nd, Sm, Eu, Tb and Lu in volcanic rock specimens from Ghana have been compared. These rock samples were examined using inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, and instrumental neutron activation analysis. The Am-241 excitation-based X-ray fluorescence accuracies were good for Y, La, Ce, Nd, Eu, and the results were comparable to inductively coupled plasma mass spectrometry and instrumental neutron activation analysis except Silver-anode X-ray tube X-ray fluorescence. This demonstrates the limitations of the tube-based X-ray fluorescence excitation system for rare earth elements analysis, primarily caused by interference between the K-series X-ray emission from the transition metals and the relatively low intensities of L-series lines of the rare earth elements. Data on the precision and accuracy of these methods were based on IAEA SOIL-7 reference material.

X-ray Diffraction and Trace Element Analyses of K/Pg Boundary Samples Collected from Agost and Caravaca, Spain

The boundary between Cretaceous and Paleogene (K/Pg) plays an important role in deciphering the Earth’s history and biological evolution from Mesozoic to Cenozoic. As such, the delineation and characterization of the boundary layer has attracted significant attention. In this study, X-ray diffraction (XRD) and elemental analyses were conducted to characterize the samples of boundary layer and the layers around Agost and Caravaca, Spain. The XRD results showed that the layers immediately above and below the boundary layer are made of limestone, while in the boundary layer, a significant increase in the clay minerals smectite, kaolinite, and illite was observed. The major element analyses revealed an increase in Si and Al contents, confirming the presence of clay minerals. The trace element analyses showed elevated concentrations of V, Cr, Ni, Zn, Pb, and Th, but not for Rb, Cu, and U. The rare Earth element (REE) analyses showed elevated La, Ce, and Nd concentrations in the boundary layer. Correlation analyses between selected trace elements and REE showed good agreements, with R2 values of about 0.9. The results agreed well with the finding in the area, except the lower contents of Rb, Cu, and U; thus, they may promote further studies to make detailed comparisons.

Gemological features of diaspore in sodra—Milas (mugla) region

Diaspore, is related to bauxite in terms of its formation mechanism. Diaspore is one of the gemstone quality stones used in jewelry and jewelry making. It is possible to come across gemstones in various regions of the world. In our country, there are gemstone deposits in all regions. In these deposits, diaspore crystals are considered very valuable. Within the scope of this study, it was aimed to determine the gemological features of the diaspore formations in Sodra (Milas-Mugla) and its surroundings, as well as to determine other minerals and their formation conditions. Main oxide, trace, and rare earth element analyses were performed on seven collected samples. The classification was made using the Al2O3-SiO2-Fe2O3 triangular variation and it was determined that bauxite samples were in the “ferric bauxite” and “bauxite” areas. SEM imaging and EDS analyzes were performed on the samples and according to this result, it was determined that the samples mainly contained O, Al, and Si. The data obtained as a result of Raman Spectroscopy were matched with the device’s own data library and it was determined that the samples taken from the Sodra region were diaspore. In addition, according to the results of the FTIR analysis performed on the faceted sample taken from the Sodra region, it was seen that the samples were compatible with the reference standards and it was scientifically proven to be a diaspore crystal with gemstone quality. During the field studies carried out in the study area, diaspore crystals were encountered in the Milas-Sodra region, together with chloritoid and muscovite, within the metabauxite formations and in the altered zones close to the metabauxite limestone contact. Rock were classified as “muscovitequartzschist,” “quartzschist” with grano-lepidoblastic texture, “micaquartzschist” with lepidoblastic texture, “phyllite” with lepidoblastic texture, and “chlorite-epidote fels” with nematoblastic texture as a result of petrographic analyzes performed on the country rock samples. It is predicted that these gemstone-quality diaspore crystals can be evaluated economically.

Tectonic Implication of the Permo-Triassic Khao Yai Mafic Volcanic Rocks in Nakhon Nayok Province, Thailand: Evidence from Geochemistry and Rare Earth Elements (REEs)

The Permo-Triassic Khao Yai Volcanics in Nakhon Nayok Province, Thailand, is a part of the Loei-Phetchabun-Nakhon Nayok Volcanic Belt. The purpose of this study is to clarify the geochemistry and REEs characteristic of Khao Yai Volcanics that is useful for identifying the paleo-environment or tectonic setting eruption in this area. The least-altered, mafic volcanic rocks from the Permo-Triassic Khao Yai volcanics, are seriate-textured to porphyritic, with variable amounts of phenocrysts/microphenocrysts. The mineral compositions include plagioclase, clinopyroxene, orthopyroxene, olivine, minor Fe-Ti oxide mineral, amphibole, apatite, biotite/phlogopite, monazite/zircon, glassy, and quartz. The geochemical characteristic of the Khao Yai Volcanics informed that the rocks had the same parental magma with different degrees of crystal fractionation. Most of the mafic volcanic rocks are subalkalic andesite on the basis of their Zr/TiO2 and Nb/Y ratios and calc-alkalic on diagrams Ti-Zr, Ti-Zr-Y, Hf-Th-Ta and Y-La-Nb. The least-altered mafic volcanic rocks have (La/Sm)cn and (Sm/Yb)cn ranging from 2.41 to 2.71 and 1.86 to 2.22, respectively. The studied calc-alkalic andesite are analogous to the Quaternary calc-alkalic dacite and andesite from Maca Volcano, Patagonian Andes and the Middle Eocene andesite from Shimokoh cauldron, SW Japan in terms of chondrite-normalized REEs and N-MORB normalized patterns. Accordingly, the studied Khao Yai volcanics have been developed in an active continental margin, formed by eastward underthrusting Paleo-Tethys, the leading edge of Shan-Thai, beneath Indochina in the Late Permian to Early Triassic. HIGHLIGHTS New tectonic model of the Permo-Triassic Khao Yai mafic volcanic rocks in Nakhon Nayok Province, Thailand The geochemistry and rare earth elements (REEs) analysis by XRF and ICP-MS The REEs analog to modern volcanic rock The classification of pre-Jurassic volcanic belt in Thailand GRAPHICAL ABSTRACT

Rare Earth Partition Characteristics and Sedimentary Diagenetic Response in Layered Argillaceous Limestone: Taking the Shale of Upper Es4 in the Nx55 Well Area as an Example

Taking the layered argillaceous limestone in the upper Es4 in the Dongying Sag as the research object, the geochemical analysis of major, trace, and rare earth elements (REEs) established the response relationship between REE distribution characteristics and sedimentary diagenesis. The average values of total light REE ( Σ LREE )/total heavy REE ( Σ HREE ) of micrite calcite and argillaceous laminae are 6.75 and 4.06, respectively. The LREEs and HREEs are differentiated, consistent with the distribution pattern of REEs in the crust. Th and U elements are more enriched in the sediments in the lacustrine sedimentary environment than in the diagenetic calcite veins. In primary sediments (argillaceous clay and micrite calcite laminae), LREEs are more enriched, HREEs are depleted, and Eu shows positive anomaly-enrichment characteristics. The LREEs and HREEs of the sparry calcite veins are lower than those of the original sediment argillaceous clay and micrite calcite, showing characteristics of a negative anomaly depletion. Sparry calcite veins originate from diagenetic fluid crystallization and precipitation and have the characteristics of low Th and U, evident positive anomalies of Sr and Eu, and substantial depletion of La. The distribution patterns of REEs within the four components of the laminated argillaceous sparry limestone reflect the order of REE distribution from primary sediment laminae (argillaceous clay and micrite calcite) to diagenetic laminae (calcite veins). Compared with the North American shale, the four components of the contact surface between the argillaceous and bright crystalline laminae, the micrite calcite, the calcite veins, and the argillaceous laminae all showed weak negative δ Ce anomalies and positive δ Eu anomalies. The fractionation degree between LREEs and HREEs reflected by La / Sm cn and Gd / Yb cn is in descending order: the interface between the argillaceous lamina and sparry calcite lamina, micritic calcite, calcite vein, and argillaceous lamina. The argillaceous laminar material has the characteristics of basalt REEs, indicating that the terrestrial debris and argillaceous lacustrine shale in the upper Es4 member of the Niuzhuang subsag are primarily derived from the basic extrusive rocks of the Qingtuozi bulge. REE differentiation is most noticeable at the interface between the argillaceous lamina and calcite vein, proving the directionality of REE differentiation from the original sedimentary lamina to the diagenetic lamina. Shale in the study area is primarily deposited below the redox interface of water at a certain depth, and the deposition rate is stable and slow, providing good conditions for preserving organic matter.

LIBS assisted PCA analysis of multiple rare-earth elements (La, Ce, Nd, Sm, and Yb) in phosphorite deposits

In the present study, the immediate detection of rare-earth elements (REEs) in phosphorite deposits has been reported using laser-induced breakdown spectroscopy (LIBS). Numerous emission lines corresponding to the REEs such as lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), and ytterbium (Yb), have been detected in the emission spectra of phosphorite-induced plasma plume. For the quantitative analysis, we employed the calibration-free LIBS (CF-LIBS), and Energy Dispersive X-ray (EDX) spectroscopy techniques. The results obtained using the CF-LIBS technique show excellent agreement with that obtained by EDX. Besides principal component analysis (PCA) was employed by incorporating the LIBS spectral data of rare earth phosphorite rocks samples containing La, Ce, Nd, Sm, and Yb emission lines. The first three PCs were observed using LIBS spectral data set showing a covariance (interpretation rate) up to 76.3%. This study suggests that LIBS yields a quick and very reliable qualitative and quantitative analysis of REEs in any geological ore sample.

Fluid evolution and petroleum accumulation in the precambrian gas reservoirs of the Sichuan Basin, SW China

Deep marine carbonates comprise one of the most significant reservoir types globally. Reconstruction of Precambrian oil reservoirs and the complex tectonism that affected Precambrian carbonate reservoirs demonstrate the complexity of the natural gas enrichment mechanism. A comparison between the fluid evolution of the well-preserved reservoirs in the central Sichuan Basin and the poorly preserved reservoirs in the southeastern Sichuan Basin offers insights into the factors that control the preservation of ancient reservoirs. We conducted geochemical analysis of the multistage cementation sequence, Raman quantitative analysis on fluid (gas) inclusions, and rare earth element (REE) analysis of diagenetic fluid environments. Hydrocarbon migration can cause variations in the diagenetic environment. Quantitative Raman measurements of the trapping pressure, trapping temperature, and composition of fluid (gas) inclusions are also useful in defining periods of gas accumulation. In situ U–Pb dating results of dolomite veins indicate that extensive dolomitization in the Sichuan Basin began during the early Cambrian. In the central Sichuan Basin, reservoir pressure evolved from normal during the Middle Jurassic to strongly overpressured during the mid-Cretaceous. Overpressure generated before Himalayan tectonism appears to be positively correlated with gas preservation. Overpressure within inclusions bearing hydrogen sulfide indicates that thermochemical sulfate reduction (TSR) does not produce intense dissolution that increases the porosity of carbonate reservoirs and reduces pore pressure. Poorly preserved reservoirs were intruded by exogenous and hydrothermal fluids but remained normally pressured. Secondary methane-rich gas inclusions record normal pressure conditions during the early Paleogene.

Genesis and Geodynamic Significance of Chromitites from the Fuchuan Ophiolite, Southern China, as Evidenced by Trace Element Fingerprints of Chromite, Olivine and Pyroxene

AbstractThe Fuchuan ophiolite is located in the northeasternmost segment of the Neoproterozoic Jiangnan orogen and consists mainly of harzburgites, with minor dunites, pyroxenite and gabbro veins and dykes. In order to investigate the genesis and tectonic setting of the Fuchuan ophiolite and chromitites, in situ analyses of unaltered chromites and silicates were carried out. Trace element analyses of unaltered chromites from the Fuchuan chromitites indicate the parental magma is of mid‐ocean ridge basalt (MORB)‐like origin, with the Ti/Fe3+#–Ga/Fe3+# diagram of chromites showing that the chromitites are a result of melt/rock interaction of MORB melts with mantle peridotites, and that the Fuchuan harzburgites present the dual features of MORB and supra‐subduction zone peridotites (SSZP). Trace and rare earth element (REE) analyses of olivines and orthopyroxenes from the Fuchuan harzburgites hint at the possibility of mantle metasomatism influenced by SSZ‐subducted fluids. Finally, integrating with previous study, the Fuchuan ophiolite and chromitites might have been formed in a back‐arc spreading ridge between the Yangtze and Cathaysia blocks during the Neoproterozoic.

Mineralization age and genesis of the makeng-style iron deposits in the Paleo-Pacific tectonic domain of South China: In situ LA-ICPMS garnet U-Pb chronological and geochemical constraints

To reveal the genesis of Makeng-style iron polymetallic deposits from SE China in the paleo-Pacific tectonic domain, a new analytical method of LA-ICPMS garnet U-Pb dating and rare Earth element analysis was conducted for the Makeng, Luoyang, Dapai and Pantian deposits. The U-Pb dating results of nine garnet skarn samples from these deposits suggested that the Makeng-style iron polymetallic deposits mainly formed during 137–130 Ma, which is consistent with the zircon U-Pb and molybdenite Re-Os ages. This study provides more direct evidence of the mineralization age and the relationship between mineralization and granite, compared with previous studies on the zircon U-Pb dating for granites in the ore fields. Rare Earth element (REE) analysis results and REE patterns of four representative garnet samples from the Makeng, Luoyang, Dapai and Pantian deposits show that they are similar to typical skarn deposits, but obvious differences in the REE distribution types indicate that the ore-forming process may be distinct due to different mineralizing fluid for these Makeng-style deposits. Our new garnet U-Pb dating and rare Earth element analysis result not only provides new evidence for the mineralization age and genesis of the Makeng-style deposits but is also of great significance to promote the application of U-Pb dating methods to research skarn type deposits.

The coal-forming environment during mass extinction in the latest permian: Evidence from geochemistry of rare Earth elements

The C1 coal of Latest Permian during mass extinction in eastern Yunnan was studied to reveal the terrestrial paleoenvironment and influence of geological events on coal-formation during mass extinction. An analysis of Rare Earth Elements (REEs) was conducted on the C1 coal from the Yantang Mine of Xuanwei, eastern Yunnan Province, which was deposited during the latest Permian. A total of 24 samples from coals, partings, roofs and floors from the C1 coal were taken from the fresh face in the underground mine. The results of the REEs analysis indicated that the total REE content (∑REE) in the C1 coal varies from 23.99 μg/g to 267.94 μg/g, averaged 122.69 μg/g. The C1 coal is enriched in light REE (LREE) relative to heavy REE (HREE), signifying the fractionation between LREE and HREE. Most samples of the coal seam C1 are depleted in Eu in various degrees and slightly depleted in Ce, especially two partings in sub-seams B1 and B3 which show the significant negative Eu anomalies. The geochemical characteristics of REE reveal that the C1 coal was deposited in a weak oxidation environment; the sedimentary environment was turbulent during the middle-later stage of coal-forming process; the C1 coal was affected by the basalt clastic materials from the Khangdian Oldland and acidic synsedimentary volcanic ash in the coal-forming period. The geochemical characteristics of Tonsteins in C1 coal are similar to those of marine Permian-Triassic boundary (PTB) volcanic ash layers in South China, which are both derived from the felsic volcanism caused by the closure of the Paleo-Tethys at the southwestern margin of the South China. Furthermore, the C1 coal was also affected by the eruption of Siberian large igneous province (SLIP) in the early stage.

Development of an analytical method for accurate and precise determination of rare earth element concentrations in geological materials using an MC-ICP-MS and group separation.

The concentration of rare earth elements (REEs) in geological materials including SLRS-6 (natural water certified reference material) and JB1b, JA1, and JG2 (Standard Rock Materials of Geological Survey of Japan) can be used as a tracer to characterize various geochemical processes in earth systems. Particularly, accurate and precise determination of rare earth element concentration in natural waters is difficult due to their extremely low concentration and the interference of polyatomic oxides. In this study, we developed a method for accurate and precise determination of the REE (particularly heavy rare earth elements) concentrations in geological materials including natural waters using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) and group separation by 2-hydroxyisobutyric acid (HIBA). The REEs were separated into light rare earth elements (LREEs, La-Ce-Pr-Nd), middle rare earth elements (MREEs, Sm-Eu-Gd-Tb), and heavy rare earth elements (HREEs, Dy-Ho-Er-Tm-Yb-Lu) by a cation-exchange column (AG50W-X8 200-400 mesh) using HIBA. The recovery rates of each REE in the natural water sample exceeded 98%, whereas the recovery rates of each REE in rock materials exceeded 95% except for HREEs. The method developed in this study can accurately measure the REE concentrations (particularly HREE) in geological materials without polyatomic oxide interference during the REE analysis by using the MC-ICP-MS and, thus, can correctly interpret the geochemical implications of REEs in geological systems. The determination of the Sr concentrations and Sr isotopic ratios of SLRS-6 CRM and JB1b, JA1, and JG2 SRMs is also reported, and they are shown to be in good agreement with the recommended values.

Radiogenic Nd in bioapatite from rare earth elements rich deep sea sediments from Central Indian Oceanic Basin and its implication in material sources

Rare Earth Element and Yttrium (REY)-rich deep sea sediments have been estimated to be a highly important potential resource. However, the main material sources that supply the huge amount of REY resources, as well as geochemical procedure determines the distinct REY patterns of these sediments, remain unclear. To fill this research gap, in this study, three sediment cores (GC02, GC04, and GC11) collected from the Central Indian Ocean Basin (CIOB) and a core (GC03) from eastern of the 90° E Ridge (NER) were sampled for mineral identification and elemental (major, trace, and rare earth elements) analyses. Fish teeth and detrital minerals were isolated from the sediments, and their 87Sr/86Sr and 143Nd/144Nd ratios were measured. Accumulation of REY is revealed in three cores of GC02, GC04, and GC11 from CIOB with mean value of 511.93 μg/g, 614.79 μg/g, and 1036.14 μg/g, respectively. Most REY rich sediment exhibit obvious to slight negative Ce abnormal, slight positive Eu and Y abnormal. The detrital fraction of the REY rich sediments exhibit less radioactive εNd values of − 8.36295 and more radioactive 87Sr/86Sr of of 0.71651. On the contrary, the fish teeth exhibit less radiogenic 87Sr/86Sr ratio of 0.70915 but more radiogenic εNd values of − 5.13511 than those of the sea water of the Indian Ocean. The results reveal that the REY-rich sediments in the CIOB are characterized by multiple material sources including weathering continental products, alteration of volcanogenic glasses, hydrothermal and marine authigenic materials. Distinct volcanogenic materials input are obvious in the CIOB evidenced with radiogenic 143Nd/144Nd ratios of the fish teeth, the wide occurrence of clinoptilolite and high Te contents contained. The volcanogenic related hydrothermal materials are then indicated to provide most part of REY for the fish teeth, which contribute the most amount of REY of the sediments. However, the terrestrial input of REY cannot be neglected, which indicates the REY-rich deep sediments were formed under multi-source supply system. The study indicated that continuous exchange of Sr between fish teeth and ambient pore water after deposition, and ambient pore water was concluded to contain an abundance of released radiogenic terrestrial Sr. However, the exchange of Nd between fish teeth and bottom sea water ceased after buried in depth. Nd ratios on the fish teeth recorded the more radioactive hydrothermal material carried by bottom seawater at the early stage of precipitation.

Radiative transition probabilities of neutral and singly ionized rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) estimated by laser-induced breakdown spectroscopy

Rare earth elements (REEs) are essential to society given their prevalence in many modern technologies. Quantitative elemental analysis of REEs is therefore a critical capability. Calibration free–laser-induced breakdown spectroscopy (CF-LIBS) is a rapidly maturing and promising approach to quantitative elemental analysis with many attractive qualities. The application of CF-LIBS to analyzing samples containing the REEs is hindered by a lack of fundamental data, specifically transition probabilities (TPs). This study seeks to help address this knowledge deficiency by reporting 967 previously unreported TPs for 13 REEs (lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The method developed in this study to estimate the TPs requires small amounts of material (a few nanograms) compared with other approaches (∼ milligrams), uses non-specialized equipment, and does not involve complicated sample preparations.

Rapid quantitative analysis of rare earth elements Lu and Y in rare earth ores by laser induced breakdown spectroscopy combined with iPLS-VIP and partial least squares.

Rare earth ores are complex in composition and diverse in mineral composition, requiring high technical requirements for the selection of rare earth ores. It is of great significance to explore the on-site rapid detection and analysis methods of rare earth elements in rare earth ores. Laser induced breakdown spectroscopy (LIBS) is an important tool to detect rare earth ores, which can be used for in situ analyses without complicated sample preparation. In this study, a rapid quantitative analysis method for rare earth elements Lu and Y in rare earth ores was established by LIBS combined with an iPLS-VIP hybrid variable selection strategy and partial least squares (PLS) method. First, the LIBS spectra of 25 samples were studied using laser induced breakdown spectrometry. Second, taking the spectrum processed by wavelet transform (WT) as the input variables, PLS calibration models based on interval partial least squares (iPLS), variable importance projection (VIP) and iPLS-VIP hybrid variable selection were constructed to quantitatively analyze rare earth elements Lu and Y, respectively. The results show that the WT-iPLS-VIP-PLS calibration model has better prediction performance for rare earth elements Lu and Y, and the optimal coefficient of determination (R2) of Lu and Y were 0.9897 and 0.9833, the root mean square error (RMSE) were 0.8150 μg g-1 and 97.1047 μg g-1, and the mean relative error (MRE) were 0.0754 and 0.0766, respectively. It shows that LIBS technology combined with the iPLS-VIP and PLS calibration model provides a new method for in situ quantitative analysis of rare earth elements in rare earth ores.

Selective micro extraction of rare earth elements and yittrium in rock samples using silica modified with xylenol orange and their determination by ICP-AES

A systematic study on the selective extraction of rare earth elements (REEs) and yttrium onto silica modified with xylenol orange (SMXO) was carried out and a scheme for the pre-concentration and separation of REEs and Y in rock samples is discussed. A simple single step preparation of silica and its modification by xylenol orange in presence of cetyltri-methylammonium bromide is enumerated. Characterisation of prepared adsorbent was carried out by surface area analysis, IR data and SEM data. REEs and Y were adsorbed onto SMXO at pH ≥ 3 and after a contact period of 30 minutes. Adsorbed REEs and Y were eluted from SMXO with 0.5% (w/v) EDTA solution. Aluminium and iron when present above 200 mg/L were interfering in the analysis of REEs. Aluminium interference was eliminated by removing it as sodium aluminate in the fusion stage of rock samples. Interference of Fe3+was avoided by reducing Fe (III) to Fe (II) using hydroxylamine hydrochloride. Separated REEs were determined by ICP-AES. The proposed method is simple, accurate and the precision is characterized by the % RSD ranges from 2.0-5.1% at the determination limit ranging from 0.2-5µg/mL.

Detrital Zircon Geochronology and Tectonic Evolution Implication of the Middle Jurassic Zhiluo Formation, Southern Ordos Basin, China

The Ordos Basin’s southern part is a composite zone made up of numerous continental blocks and has long been influenced by surrounding tectonism. However, only a few studies have investigated the existence of southern provenance supply and the basin’s southern boundary in the Middle Jurassic Zhiluo Formation. Based on sandstone detrital zircon U-Pb dating and zircon rare earth element analyses, net-sand ratio maps, paleocurrent direction and the field outcrop survey, this study establishes the source area and boundary of the Zhiluo Formation in the southern basin, and discusses the tectonic events. The study shows that the four main age peaks in the detrital spectra occurs at 2283 Ma, 1788 Ma, 432.5 Ma and 218.7 Ma, with a few of the zircons dated at 794.5–1235.2 Ma. The North Qilian orogenic belt (N-QLOB), the western part of the North Qinling orogenic belt (NQOB), and the southern margin of the North China Block (SNCB) contributed to the provenance. According to an integrated analysis of the provenance and tectonic background of continental blocks in the basin’s southern margin, the boundary of the basin in the depositional period of the Zhiluo Formation should reach the N-QLOB in the southwest, the NQOB in the south, and the Sanmenxia–Lushan fault belt in the southeast. On the basis of the aforementioned findings, the tectonic evolution of the continental blocks at the southern periphery of the Ordos Basin was restored.

Discrimination of thermodynamic and kinetic contributions to the heavy rare earth element patterns in metamorphic garnet

AbstractVariations of rare earth element (REE) concentrations in metamorphic garnet are an important source of information of geodynamic and geochemical processes in the deeper Earth. In order to extract this information, the thermodynamic equilibrium and kinetic contributions of the REE uptake in garnet must be distinguished and quantified. Utilizing high‐resolution trace element and μ‐Raman mapping together with combined thermodynamic–geochemical–diffusion models, we demonstrate that the equilibrium and kinetic aspects of the REE uptake in metamorphic garnet can be discriminated by interpreting 2D trace element mapping in a single sample. The heavy (H) REE (Tb to Lu) zoning in the investigated garnet from a high‐pressure blueschist comprises an inner part with an overall decrease from core to inner rim, followed by a concentric zone of HREE enrichment and a drastic HREE decrease towards the outermost rim. The central peak in the garnet core decreases in intensity with decreasing atomic number of the REE. The broad overall shape of this pattern resembles those often observed in metamorphic garnet from different rock types and tectonic settings. Superimposed on this trend is a concentric pattern of minor recurring fluctuations in the HREE concentrations with at least six regularly spaced sets of peaks and troughs along the entire garnet radius. Comparison of the observed inclusion suite, the trace element maps and thermodynamic–geochemical models show that the inner part with decreasing HREE concentrations results from fractional garnet growth in an unchanged mineral assemblage, whereas the REE enrichment zone is caused by the breakdown of titanite. We suggest that the width of the central peak is controlled by the bulk permeability of the interconnected transport matrix and the fraction of matrix minerals that the garnet equilibrates with. The superimposed REE fluctuations result from changing element transport properties of the host rock and mark recurring changes from equilibrium REE uptake to transport‐limited REE uptake in garnet. Such fluctuating element transport properties can be best explained by pulse‐like fluid fluxes that rhythmically change the interconnectivity of the intercrystalline transport matrix. Increasing numbers of published spatially highly resolved REE analyses show that such trace element fluctuations are common in metamorphic garnet indicating that recurring changes in rock permeabilities due to pulsed fluid fluxes are a common phenomenon during metamorphism.

Origin and diagenetic evolution of dolomites in Paleogene Shahejie Formation lacustrine organic shale of Jiyang Depression, Bohai Bay Basin, East China

The origin of dolomite in Shahejie Formation shale of Jiyang Depression in eastern China were studied by means of petrologic identification, compositional analysis by X-ray diffraction, stable carbon and oxygen isotopic composition, and trace element and rare earth element analyses. The results show that the development of dolomite is limited in the lacustrine organic rich shale of Shahejie Formation in the study area. Three kinds of dolomite minerals can be identified: primary dolomite (D1), penecontemporaneous dolomite (D2), and ankerite (Ak). D1 has the structure of primary spherical dolomite, high magnesium and high calcium, with order degree of 0.3-0.5, and is characterized by the intracrystalline corrosion and coexistence of secondary enlargement along the outer edge. D2 has the characteristics of secondary enlargement, order degree of 0.5-0.7, high magnesium, high calcium and containing a little iron and manganese elements. Ak is characterized by high order degree of 0.7-0.9, rhombic crystal, high magnesium, high calcium and high iron. The micritic calcite belongs to primary origin on the basis of the carbon and oxygen isotopic compositions and the fractionation characteristics of rare earth elements. According to the oxygen isotopic fractionation equation between paragenetic dolomite and calcite, it is calculated that the formation temperature of dolomite in the shale is between 36.76-45.83 °C, belonging to lacustrine low-temperature dolomite. Based on the maturation and growth mechanism of primary and penecontemporaneous dolomite crystals, a dolomite diagenetic sequence and the dolomitization process are proposed, which is corresponding to the diagenetic environment of Shahejie Formation shale in the study area.