Rare Earth Elements(La,Ce,Pr)Modified Co/NC Catalyst for Efficient and Stable Ammonia Decomposition to Hydrogen Production

Co/NC catalysts modified with rare earth elements(La,Ce,Pr)were prepared by pyrolysis of rare earth elements doped ZIF-67.The experimental results show that the modification of rare earth elements significantly improves the ammonia decomposition activity and stability of the Co/NC catalyst.The La-Co/NC catalyst can achieve an 82.3%ammonia decomposition and 18.4 mmol hydrogen production rate at 550℃with a GHSV of 20000 cm^(3)·h^(-1).Furthermore,no obvious performance degradation is observed after 72 hours of reaction for all rare earth elements modified catalysts.It is shown that the modification of rare earth elements significantly improves the surface alkalinity and surface chemical state of the catalyst,and thus improves the ammonia decomposition activity of the catalyst.A new type of high-performance ammonia decomposition Co-based catalyst is proposed,and the promoting effect of rare earth elements on the activity of ammonia decomposition is revealed.

Association between Exposure of Rare Earth Elements and Outcomes of In Vitro Fertilization-Embryo Transfer in Beijing

Objective The study aimed to investigate the impact of rare earth elements(REEs)exposure on pregnancy outcomes of in vitro fertilization-embryo transfer(IVF-ET)by analyzing samples from spouses.Methods A total of 141 couples were included.Blood and follicular fluid from the wives and semen plasma from the husbands,were analyzed for REEs using inductively coupled plasma mass spectrometry(ICP-MS).Spearman's correlation coefficients and the Mann–Whitney U test were used to assess correlations and compare REE concentrations among three types of samples,respectively.Logistic models were utilized to estimate the individual REE effect on IVF-ET outcomes,while BKMR and WQS models explored the mixture of REE interaction effects on IVF-ET outcomes.Results Higher La concentration in semen(median 0.089 ng/mL,P=0.03)was associated with a lower fertilization rate.However,this effect was not observed after artificial selection intervention through intracytoplasmic sperm injection(ICSI)(P=0.27).In semen,the REEs mixture did not exhibit any significant association with clinical pregnancy.Conclusion Our study revealed a potential association between high La exposure in semen and a decline in fertilization rate,but not clinical pregnancy rate.This is the first to report REEs concentrations in follicular fluid with La,Ce,Pr,and Nd found at significantly lower concentrations than in serum,suggesting that these four REEs may not accumulate in the female reproductive system.However,at the current exposure levels,mixed REEs exposure did not exhibit reproductive toxicity.

Changes in Sediment Sources in the Southern Muddy Area of Weihai,China,Since the Late Pleistocene:A Record from Rare Earth Elements

The small muddy areas developed in the southern Shandong Peninsula have attracted increasing attention from researchers because of complex changes in sediment sources driven by sea-level fluctuations and land-sea interactions since the late Pleistocene.This study investigates the evolution of sediment sources and their responses to environmental changes since the late Pleistocene,using core WHZK01 collected from the nearshore muddy area in southern Weihai for rare earth element(REE)analysis.In doing so,this work highlights the changing patterns of material sources and the primary control factors.The results reveal that the sedimentary deposits in core WHZK01 exhibit distinct terrestrial characteristics.Discriminant function analysis(F_(D))and source discrimination dia-grams both suggest that the primary sources of these deposits are the Yellow River and adjacent small and medium-sized rivers,although the sources vary among different sedimentary units.Furthermore,the DU3 layer(17.82-25.10 m)displays typical riverine sedimentation,dominated by terrestrial detrital input,primarily from the local rivers,namely the Huanglei and Muzhu Rivers.The material in the DU2 layer(14.91-17.82 m)is mainly influenced by a mixture of the Qinglong and Yellow Rivers.The DU1 layer(0-14.91 m)is influenced by sea-level changes during the Holocene,with the Yellow River being the primary source,although there is also some input from local rivers.The changes in sea level during the Holocene and the input of Yellow River material carried by the coastal currents of the Yellow Sea are identified as the main controlling factors for the changes in material sources in the study area since the late Pleistocene,with small and mediumsized rivers also exerting some influence on the material sources.The above mentioned findings not only contribute to a better understanding of the source-sink systems of the Yellow River and adjacent small and mediumsized rivers but also deepen our understanding of the late Quaternary land-sea interactions in the Shandong Peninsula.

Geochemical characterization of rare earth elements in sediment profiles from the Oualida lagoon(Morocco)

The present work assesses the temporal distribution pattern and geochemical changes of rare earth elements and Yttrium, Scandium, Thorium, and Uranium delivery into the Oualidia lagoon. Two sediment cores were retrieved from the Oualidia lagoon and analyzed using neutron activation analysis. The results indicated that heavy rare earth elements are slightly enriched the sediment cores over light rare earth elements. The highest values of REEs were recorded in the top layers of the cores and depleted with depth, suggesting a possible change in factors controlling their accumulation, including mechanical, chemical, and environmental parameters such as weathering intensity, grain size, and Fe-Mn oxides. The sediments display positive Ce anomalies, which are probably related to the submarine weathering process and detrital input. Noting also the variation of hydrodynamics conditions and confinement of the upstream part of the lagoon played a key role in changing the sediment origins.Thus, further investigation of REEs origin in the Oualidia lagoon sediment is required to identify their sources,provenances, and the factors controlling their spatial and vertical distributions. However, these results provide baseline data of occurring changes in REEs geochemical composition and constitute a typical study case to understand the link between sedimentary and geochemistry processes in a lagoonal ecosystem.

Determination of 16 Rare Earth Elements in Banana by Microwave Digestion and ICP-MS

[Objective] This study aimed to investigate the residues of rare earth ele-ments in Guangxi banana from banana-producing area with application of rare earth fertilizers and evaluate the safety of using rare earth fertilizers in banana production. [Method] HNO3＋H2O2 mixed acid system with high pressure airtight microwave di-gestion sample pretreatment method and ICP-MS technology were used, to establish a determination method of 16 rare earth elements in banana samples, including Sc45, Y89, La139, Ce140, Pr141, Sm147, Eu153, Gb157, Tb159, Nd144, Dy163, Ho165, Er166, Tm169, Yb172 and Lu175. [Result] Different standard curves present-ed good linearity. Detection limit of the instrument was 0.002-0.01 μg/L; detection limit of the method was 0.1-0.6 μg/kg; recovery rate of standard addition was 94.5%-116%; relative standard deviation was 2.02%-14.21%. [Conclusion] This method has many advantages, such as simple mass spectrogram, high sensitivity and high selectivity, accurate quantification, high precision and accuracy, simple operation, high reproducibility and high recovery rate, which is suitable for the detection of rare earth elements in banana and other fruits, with certain theoretical and applicable val-ue for guiding banana production and high-efficient planting.

Simultaneous Determination of Trace Rare Earth Elements and Other Elements in High Purity Terbium Oxide (Tb_4O_7) by ICP-AES After HPLC Separation Using P507 Resin

This article describes a new method for the simultaneous determination of trace rare earth elements (REEs) and non rare earth elements (NREEs) in high purity terbium oxide by ICP-AES after HPLC separation using P507 resin. The chromatographic separation of the analytes from the matrix using dilute nitric acid as mobile phase was studied. The experimental results showed that a favorable separation of trace metals (Cu and Gd) from the matrix (Tb) can easily be achieved by elution with dilute nitric acid within 25 min. The proposed method was applied to the determination of trace metals (Ca, Cu, Mg, Mn, Ni, Si, La, Ce, Pr, Nd, Sm, Eu and Gd) in high purity terbium oxide. The detection limits (DLs) for the analytes ranged from 0.4-4.0 μg\5g -1, and the recoveries are from 78%-105%.

Some New Results from the Electron Theory on the Elastical of Alkahoe Earth Metals and Rare Earth Elements

With the introduction of Poisson's ratio in the expression of Young's modulus,nearly all the theoretical values of the various elastic moduli for the alkaline earth metals and rare earth elements can be greatly refined, with the single exception of the theoreticalvalue of Young's modulus for Pr which is slightly increased This points to the validityof the new theory, that the bulk modulus is independent of the Poisson's ratio, and further that the valency electron structures of solids as determined by Yu's theory are correct.

Recovery of iron and rare earth elements from red mud through an acid leaching-stepwise extraction approach

A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can reach up to 95.9%,82.1%,68.3%,93.3%,82.3%,96.9%,98.3%and 95.6%,respectively,under the optimal condition in the leaching process.Aliquat 336 showed excellent extraction performance of iron in chloride-rich solution,and the maximum extraction efficiency can reach over 96%in one time extraction while the loss of other metals was less than 10%,under the condition of Aliquat 336 concentration(v/v)of 30%,aqueous-organic ratio of 1.0 and extraction time of 20 min.Furthermore,P204 can effectively extract the scandium while Al and most other REEs remain in the aqueous phase.This approach may provide a new insight for the recovery of valuable resources from red mud.

A new type of rare earth elements deposit in weathering crust of Permian basalt in western Guizhou, NW China

A new type of rare earth elements （REEs） deposit was discovered from the gaolinite mudstone in the weathering crust of Permian basalt, Bijie region, western Guizhou, China. It contained ∑RE2O3 0.065%-1.086%. This type of REEs deposit was widely distributed with steady horizon and thickness of 3-4 m. The ore-bearing weathering crust （kaolinite） of the three discovered REEs deposits belonged to the third episode of the Emeishan basalt eruption. The new type of REEs deposit was suggested that basalt （tuff） weathering could lead to the enrichment of the rare earth elements. Therefore, it is of important economic significance to explore REEs deposits in the weathering crust of basalt （tuffs） in Yunnan, Guizhou, and Sichuan Provinces.

A Survey of 16 Rare Earth Elements in the Major Foods in China

Objective The aim of this survey was to investigate the level of contamination of the most consumed foods in China with 26 rare earth elements （REEs）, and to provide the basic data for establishing and revising food safety standards for REEs. Methods Sixteen REEs in foods were measured by inductively coupled plasma-mass spectrometry （ICP-MS） in the labs of the Centers for Disease Control and Prevention of four provinces and two municipalities, during 2009-2020. Results 2 231 samples were analyzed and 29 221 concentration data of 16 REEs were collected. The REEs levels in the investigated foods varied significantly. The concentrations of cerium （Ce）, dysprosium （Dy）, yttrium （Y）, lanthanum （La）, and neodymium （Nd） were relatively high, while the remaining eleven REEs were at low levels. The mean values of total rare earth element oxides （REOs） in cereals, fresh vegetables, fresh aquatic products, fresh meats and eggs varied from 0.052 mg/kg to 0.337 mg/kg. Conclusion 16 REEs in the major foods were at very low contamination levels in the investigated regions.

From mantle to critical zone:A review of large and giant sized deposits of the rare earth elements

The rare earth elements are unusual when defining giant-sized ore deposits,as resources are often quoted as total rare earth oxide,but the importance of a deposit may be related to the grade for individual,or a limited group of the elements.Taking the total REE resource,only one currently known deposit（Bayan Obo） would class as giant（〉1.7×10^7 tonnes contained metal）,but a range of others classify as large（〉1.7×10^6 tonnes）.With the exception of unclassified resource estimates from the Olympic Dam 10 CG deposit,all of these deposits are related to alkaline igneous activity- either carbonatites or agpaitic nepheline syenites.The total resource in these deposits must relate to the scale of the primary igneous source,but the grade is a complex function of igneous source,magmatic crystallisation,hydrothermal modification and supergene enrichment during weathering.Isotopic data suggest that the sources conducive to the formation of large REE deposits are developed in subcontinental lithospheric mantle,enriched in trace elements either by plume activity,or by previous subduction.The reactivation of such enriched mantle domains in relatively restricted geographical areas may have played a role in the formation of some of the largest deposits（e.g.Bayan Obo）.Hydrothermal activity involving fluids from magmatic to meteoric sources may result in the redistribution of the REE and increases in grade,depending on primary mineralogy and the availability of ligands.Weathering and supergene enrichment of carbonatite has played a role in the formation of the highest grade deposits at Mount Weld（Australia） and Tomtor（Russia）.For the individual REE with the current highest economic value（Nd and the HREE）,the boundaries for the large and giant size classes are two orders of magnitude lower,and deposits enriched in these metals（agpaitic systems,ion absorption deposits） may have significant economic impact in the near future.

Effect of rare earth elements addition on thermal fatigue behaviors of AZ91 magnesium alloy

Influences of rare earth （RE） elements addition on thermal fatigue behaviors of AZ91 alloy were studied. Repeated heating and cooling cycles were applied on the samples at 170 and 210℃ to develop thermal fatigue cracks. Crack growth mechanisms and microstructural influences were investigated by optical and scanning electron microscopy （SEM） as well as energy dispersive X-ray spectroscopy （EDS）. Thermal fatigue behaviors were observed to improve successively by addition of the RE up to 2wt.%. This improvement was attributed to the consummation of aluminum in melt by precipitation of the needle shaped AII1RE3 phases. This process was attributed to the reduction of MglTAl12 phase volume fraction and consequent decrease of the brittle Mg/MglTAl12 interface which was the main reason for weak thermal properties of the alloy at rather high temperatures. Further additions of RE, however, reduced the thermal shock resistance of the samples by increasing the mean length of the brittle needle shaped phases.

A review of fractionations of rare earth elements in plants

Studies were carried out on several aspects of rare earth elements （REEs）, such as the theory and practice of their applications in agriculture, their geochemical behaviors in natural and agricultural ecosystems, the mechanisms for the increase of crop yield using REE fertilizer, and their toxicology. However, limited knowledge was available for the transfer processes and the features and mechanisms of distribution and fractionations of REEs inside plants. The characteristics of REE fractionations in plants can be used to ＂trace＂ the pathway of REE transportation from soils （solution） to plants. A better understanding of the mechanisms of REE fractionations was helpful to investigate the controlling factors, including both the internal and the external ones. The characteristics and mechanisms of REE fractionations in plants and their significance were reviewed. Furthermore, the prospect for these fields was discussed, in hope of providing a new way in studying the bioavailability of REEs and heavy metals.

Rare earth elements distribution in marine sediments of Malaysia coasts

In the east coast Peninsular Malaysia region,sediments are transported by several rivers from the east Malaysia into the South China Sea estuary.In the vicinity of the five river estuaries core sediments were collected in order to investigate rare earth elements(REEs) profile.Core sediments were divided into strata of between 2 to 4 cm intervals and prepared for analyzing by ICP-AES.REE concentrations of 54.3 μg/gr at 24–26 cm in EC4 increased to 114.1 μg/gr at 20–22 cm in EC5.The measured concentration of ...

Accumulation and Fractionation of Rare Earth Elements in a Soil-Wheat System

Time series bioaccumulation of rare earth elements （REEs） in field-grown wheat with and without a dressing of extraneous REE fertilizer at different growth stages and fractionation of REEs during their transport in a soil-wheat system were determined. Time-dependent accumulation of extraneous REEs was found in different parts of wheat. An upward transport of extraneous REEs from roots to shoots under a soil dressing and a downward transport from leaves to roots with a foliar dressing were also observed. Moreover, fractionation of REEs occurred in the soil-wheat system. Compared to the host soil a positive Eu anomaly in the stems and grains as well as heavy REE enrichment in the grains were found. The ability of the different wheat organs to fractionate Eu from the REE series was ranked in the order of sterns 〉 grains 〉 leaves 〉 roots.

Effect of Rare Earth Elements on Erosion Resistance of Nitrocarburized Layers of 38CrMoAl Steel

Effect of rare earth elements (RE) on erosion resistance of nitrocarburized layer of 38CrMoAl steel was investigated. The results indicate that significant improvement occurs in erosion resistance of nitrocarburized 38CrMoAl steel by introducing RE during nitrocarburizing processing as compared with conventional nitrocarburizing processing. Results of mechanical testing show that both hardness and impact toughness of RE-nitrocarburizing layer of 38CrMoAl steel increase as compared with the conventional one. Optical microscopy reveals that there is improvement in the nitrocarburized layer attributed to the introduction of RE, which results in improvement in erosion resistance. Surface morphology observation of tested samples reveals that predominantly furrow-like peelings from plastic deformation are observed for RE nitrocarburizied 38CrMoAl steel, while the furrow-like peeling with initial cross crack and large grinding peelings were observed for conventionally nitrocarburized samples.

Effect of Rare Earth Elements on Anisotropy and Microstructure of Al-Li Alloy 2195 Sheets

For the purpose of decreasing the applied limitation resulting from the anisotropic mechanical property of Al-Li alloy 2195, this study employed a complex heat treatment process, involving the pre-tension, thermo-infiltration of the rare earth element Ce, solution treatment, and artificial aging technology. The results indicate that the infiltration of rare earth element Ce benefits the abatement of anisotropy of Al-Li alloy 2195 sheet, in contrast with that of the normal heat treatment process. The gradient of the Vickers-hardness decreases at least 50% through the thickness, and the tensile strength in the rolling direction also increases significantly. If Ce was infiltrated into the alloy under the optimum pre-deformation, the yield strength （σ0.2） increased by 30 MPa while the tensile strength （σb） enhanced by 25 MPa compared to the rare earth free samples. Meanwhile, the fractography illustrated that the fracture surface of the sample became more desirable.

Anomaly and geochemistry of rare earth elements and yttrium in the late Permian coal from the Moxinpo mine,Chongqing,southwestern China

The rare earth elements and yttrium(REY)of the K2 coal from the Moxinpo mine,Chongqing,were determined using inductively coupled plasma mass spectrometry(ICP-MS).The results show that REY are enriched in the K2 coal,with the average content up to 462 lg/g,much higher than average values of most coals in the world.The REY distribution patterns indicate that the light REY is enriched and show a well-pronounced Eu minimum.The fractionation of individual light-REY is higher than that of the heavy-REY.The REY distribution through the K2 coal seam shows that the top and bottom portion of the coal seam have a lower content of REY than the middle portion.Goyazite and rhabdophane were identified with a scanning electron microscope equipped with an energy-dispersed X-ray spectrometer(SEM-EDX).The REY distributions through the coal seam,SEM-EDX data and the correlation analysis between ash yields and the concentrations have revealed that the REY mainly occurs in the organic matter.The K2 coal is a potential rare-metal resource due to its high REY contents,and the coal ash could be regarded as a new and promising raw material for recovery of REY as a by-product.

Geochemistry of rare earth elements in groundwater from deep seated limestone aquifer in Renlou Coal Mine,Anhui Province,China

Rare earth element （REE） concentrations were measured by ICP-MS for groundwater collected from deep seated Taiyuan Fm limestone aquifer （from -400 to -530 m） in Renlou Coal Mine, northern Anhui Province, China. It can be concluded that the groundwater is warm （34.0-37.2 ℃） C1-Ca, Na type water with circum-neutral pH （7.35-8.28） and high total dissolved solids （TDS, 1 746-2 849 mg/L）. The groundwater exhibits heavy REEs enrichment relative to light REEs compared with Post Archean Average Shale （PAAS）, as well as their aquifer rocks （limestone）. The enrichment of REEs is considered to be controlled by terrigeneous materials （e.g. zircon） in aquifer rocks, whereas the fractionation of REEs is controlled by marine derived materials （e.g. calcite）, to a less extent, terrigeneous materials and inorganic complexation. The Ce anomalies normalized to PAAS and aquifer rocks are weak, which probably reflects the signature of the aquifer rock rather than redox conditions or pH. The similarities of REE patterns between groundwater and aquifer rocks imply that aquifer rocks play important roles in controlling the REE characteristics of groundwater, and then provide a probability for discrimination of groundwater sources by using REEs.

Separation and Enrichment of Rare Earth Elements in Phosphorite in Xinhua,Zhijin,Guizhou

The phosphorite ores-deposits rich in rare earth elements(REE) in Zhijin, Xinhua, Guizhuo occurs in the early Cambrian Meishucun and at the bottom part of Qiongzhusi stage (the upper layer of phosphorites), belonging to Yangzi stratum section. The living creature scraps was proved existent in dolomitic-phosphorites by experiments, The REE could be extracted to provide the worthy data for the further using. Adopting the HNO3 to extract REE, through the ion exchange method, the REE recovery rate could be reached 85.44% , having certain reference value.