Neutron activation analysis of deep sea sediments from the regions near Japan

Eighteen trace elements, including seven rare earth elements (REEs), and major and minor elements in the sediment samples from the Japan Sea and the northwestern Pacific near Japan were determined with instrumental neutron activation analysis (INAA). Most REE patterns (chondrite-nomalized) of the sediments were nearly identical to the patterns of terrigenous materials without cerium anomaly whereas the La/Yb ratio varied with the site locations. The variation of the La/Yb ratio of the sediments may indicate the regional variation of the mixing proportion of the terrigenous materials from the continent to the materials from the volcanic island arcs including the Japanese islands. The Th/Sc ratio of the sediments tended to increase with distance from the island-arc volcanism. Regional variation of the Th/Sc ratio may indicate variation of amount of the continental terrigenous materials supplied to the sediments.     

Amazon estuary — assessment of trace elements in seabed sediments

The interactive processes operating on the continental shelf adjacent to the river mouth control the amount and the characteristics of the Amazon discharge reaching the Atlantic Ocean. In this study, the distribution of trace elemental concentrations, with emphasis to the rare-earth elements, in sediment cores collected at several stations from the Amazon continental shelf during the falling water period was investigated by instrumental neutron activation analysis. Cores from the terrigenous and blue water zones have relatively uniform REE concentrations throughout the profile. Cerium anomalies for samples of the upper section of the eight stations are consistently positive and of high values (normally >2). Similar variation in the elemental concentration ratios between the seabed sediments and Amazon River suspended sediments was seen for stations located in the biogenic and blue water zones, with an enrichment for Ce, Sm, Fe, Th, and Sc and a depletion for the La, Eu, Tb, Yb, Co, Cr, Cs, Hf, Ta, and Zn. The shale-normalized REE patterns from shelf sediments are enriched in LREE relative to HREE, with enrichment factors varying from 1.5 for stations near the river mouth (terrigenous zone) to 1.9 for stations located far in the blue water zone. Published data for the Amazon River suspended sediment agree remarkably well with this observation of LREE-enrichment.     

Rare earth elements determination and distribution patterns in sediments of a polluted marine environment by instrumental neutron activation analysis

Results obtained from the analysis of sediment core samples taken froma fairly polluted marine environment were analyzed for the REE contents todetermine the concentrations of La, Ce, Sm, Eu, Tb, Dy and Yb using instrumentalneutron activation analysis. Core samples were divided into strata of between2 to 3 cm intervals and prepared in the powdered form before irradiating themin a neutron flux of about 5.0 . 10¹² n . cm ^—2s ^—1 in a Triga Mark II reactor. Down-core concentration profilesof La, Ce, Sm, Eu, Tb, Dy and Yb in 3 core sediments from three sites areobtained. The shale-normalized REE pattern from each site was examined andlater used to explain the history of sedimentation by natural processes suchas shoreline erosion and weathering products deposited on the seabed and furnishingsome baseline data and/or pollution trend occurring within the study area.The shale-normalized REE patterns also showed that LREE in the sediment samplesexhibit enrichment relative to HREE particularly, La and Sm showing enrichmentcompared to the ratios in shale. REE concentrations of 124 µg/g at thesurface of sediment collected at two of the three sites were found to decreaseto 58 and 95 µg/g, respectively. This was of particular interest whenit is used to explain the anomalies occurring in the marine sediment as aresult of geochemical processes over a long period of time. Changes in concentrationsfrom surface to bottom of the sediments ratioed to Sm concentrations and thecorrelation between concentrations of Sm and these elements were also investigatedand correlation coefficients were calculated for all REEs and sites. Validationof the method used was done using a Soil-7 SRM.     

Distribution of rare earth elements in the estuarine and coastal sediments of the Daliao River System, China

The Daliao River System (DRS) estuary in Liaodong Bay features a highly industrial, urbanized, and agricultural catchment. The objective of this study was to determine the content, behavior, and distribution of the rare earth elements (REEs) in the estuarine and coastal sediments. To this end, 35 sediment samples were collected from the estuarine and coastal area and analyzed for REEs, Fe, Al, and Mn. The mean concentrations in mg kg^?1 of the sediments were 33.4 (La), 64.1 (Ce), 7.9 (Pr), 29.0 (Nd), 5.4 (Sm), 1.2 (Eu), 4.2 (Gd), 0.78 (Tb), 4.0 (Dy), 0.84 (Ho), 2.3 (Er), 0.40 (Tm), 2.3 (Yb), and 0.37 (Lu). The REE concentrations in the sediments were significantly correlated with one another (r ²  = 0.959–0.988) and the concentrations of Fe, Al, and Mn (r ²  = 0.768–0.870). The total concentration ∑REE ranged from 73.5 to 203.5 mg kg^?1, with an average of 156.0 mg kg^?1 being observed, and generally higher in the estuarine sediments than in the coastal sediments, most likely due to the salt-induced coagulation of river colloids and subsequently their accumulation at the estuarine bottom. The ratio of light REEs (∑LREE) to heavy REEs (∑HREE) was 9.4. Chondrite-normalized REE distributions were observed to be similar for the estuarine and coastal sediments, riverine suspended particles, and watershed soils of the DRS with higher LRRE enrichment than HREE and greater Eu depletion than Ce depletion. These results demonstrate that neither geochemical processes that carry soils to estuarine sediments nor long-term industrial and agricultural activities alter the distribution or fractionation of the REEs in the study area.     

Rare earth element phase distributions in a deep-sea carbonate sediment

Northeastern Atlantic sedimentary rare earth element (REE) (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) phase associations among CaCO₃, authigenic and lithogenic material are estimated from total sediment REE, Al, Ca, Si, Mn and Co abundances using a linear correlation technique. Phase associations were also determined using a selective chemical leaching technique specific for CaCO₃+exchangeable cation, easily reducible oxyhydroxide and residual material. Results suggest that 25–50% of the REE associated with the clay material are exchangeable cations and 20–35% of the total 3+REE and 4% of the total Ce reside in coatings on the CaCO₃ tests.     

Concentrations of rare earth elements in sediments,mussels and fish from a Danish marine environment,Lillebaelt

Results for the content of the rare earth elements (REE), La, Ce, Nd, Sm, Eu, Tb, Yb and Lu in sediments, mussels and fish are presented for an area polluted by REE. The REE are emitted with the process waste water stream from a fertilizer production plant. The method of analysis has been INAA. An attempt to combine the INAA with a simple destruction/preconcentration method is described.     

Rare earth elements determination and distribution patterns in surface marine sediments of the South China Sea by INAA,Malaysia

Results obtained from the analysis of sediments surface samples taken from rivers mouth and polluted marine environment were analyzed for REE contents to determine the concentrations of La, Ce, Sm, Eu, Tb, Dy, Lu and Yb using instrumental neutron activation analysis. Thirty surface samples were collected from ten sites in the coastal marine sediments of the South China Sea along 957 km stretch of the east coast of Peninsular Malaysia. The samples prepared in the powdered form before irradiating them in a neutron flux of ~4 × 10¹² n cm⁻² s⁻¹ at 750 kW power using the TRIGA Mark II research reactor at Malaysian Institute for Nuclear Technology (MINT). Results of the total concentration are used to establish baseline data in environmental pollution assessment and to develop the correlations between the Ce/Ce* anomalies and the distribution patterns of some the light rare earth elements (LREEs) and the heavy rare earth elements (HREEs). The Chondrite-normalized REE pattern from each site examined and used to explain the sedimentation patterns by anthropogenic activities and by natural processes such as shoreline erosion, weathering deposits. Shale-normalized (NASC) patterns suggest enrichment of LREEs relative to the HREEs with a positive Ce/Ce* anomaly. Validation of the used method was done using a Soil-7 SRM.     

Extraction of rare-earth elements from nitrate solutions by fullerene black impregnated with tetraphenylmethylenediphosphine dioxide

The distribution of trace amounts of La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y nitrates between HNO₃ aqueous solutions and fullerene black (a product of electric are evaporation of graphite) impregnated with tetraphenylmethylenediphosphine dioxide (L) as a function of the concentrations of HNO₃ in the aqueous phase and L in the sorbent phase was considered. It was shown that REE(III) ions pass into the sorbent phase in the form of Ln(NO₃)₃L₃ solvated nitrates; the efficiency of extraction of these ions decreases with an increase in the REE atomic number in the periodic table.     

Heteroleptic polypyrazolylborate derivatives of the lanthanide ions. The synthesis of acetylacetonate derivatives and the molecular structures of [Ln{HB(C3N2H3)3}2{MeC(O)CHC(O)Me}] (Ln = Ce,Yb)

The air and moisture stable complexes [Ln{HB(C₃N₂H₃)₃}₂{MeC(O)CHC(O)Me}] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Yb, Lu, Y), have been prepared and characterized. The molecular structures of the compounds with Ln = Ce and Yb reveal that a substantial distortion of the coordination geometry found for Ce³⁺ is necessary to allow the ligand set to accommodate the smaller Yb³⁺ ion.     

Raman Spectroscopic Study of Rare Earth Chlorides in Alkali Chloride Eutectic Melts

Raman spectra of rare earth (REE: rare earth elements) trichloride (REE = Y, La, Ce, Pr, Sm, Gd, Dy, or Yb) dissolved in alkali chloride eutectic melts (LiCl‐KCl, LiCl‐RbCl, and LiCl‐CsCl) were measured at 793 K. The spectra showed polarized peaks centered around 240–270 cm^–1, which were identified as the totally symmetric stretching vibration (ν₁) of the octahedral REECl₆^3–. The ν₁ frequency increased with the polarizing power of the trivalent REE ions. The change in the ν₁ frequency was found to be larger for lighter lanthanides. This was attributable to the distortion of the O_h symmetry of REECl₆^3–.     

Extraction of rare earth elements with phosphoryl-containing lariat crown ether in the presence of ionic liquids

Interfacial distribution of rare earth elements (REE) La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y between aqueous solutions of their nitrates and solutions of the lariat crown ether 1,4,10,13-tetraoxa-7,16-diaza(diphenylphosphinylmethyl)cyclooctadecane in dichloroethane was studied in the presence of the ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide. The stoichiometry of extracted complexes was determined; the effect of HNO₃ concentration in the aqueous phase and the nature of extractant and ionic liquid on the extraction efficiency of REE(III) was considered.     

Determination of rare earth elements in soils and sediments by inductively coupled plasma atomic emission spectrometry after cation-exchange separation

The influence of matrix elements such as Ba, Ca, Fe, K, Na and Ti, on the inductively coupled plasma atomic emission spectrometry determination of the rare earth elements in soils and sediments is investigated and analytical lines with minimal interferences are chosen. The analysis of certified reference materials by two calibration methods (pure rare earth solutions and IAEA-Soil 5) and after cation-exchange proved that calibrations with IAEA-Soil 5 increase the number of accurately determined rare earth elements (REE), permitting the instrumental determination of Ce, Eu, La, Nd, Tb, Yb and Y in soils and some sediments. The cation-exchange procedure permits the determination of 12 REE with very good accuracy (below 10%) and detection limits varying between 0.05 (Eu, Tb, Yb) and 0.5 (Er) mg kg(-1).     

湖南辰溪特高有机硫煤的稀土元素特征及其成因

采用高分辨率电感耦合等离子质谱(HR-ICP-MS)技术测定辰溪晚二叠世高有机硫(7.75%)煤中的稀土元素(REEs)。辰溪煤中∑REE变化较大,从38.84 μg/g至305.85 μg/g,加权平均值为104.57 μg/g,高于世界煤均值,与中国煤相近。辰溪煤中有明显的Ce负异常(δCe=0.74~0.84)和Eu的负异常(δEu=0.55~0.69)。煤层剖面上稀土元素含量和分布模式的变化反映了成煤环境的波动,从底板到顶板陆源物质的影响减弱,而海水的影响增强。沉积环境的阶段性变化是导致剖面上下有机硫与黄铁矿硫比值相差悬殊的原因。辰溪煤中稀土元素与铁呈现了显著的正相关性(n=11,r=0.95),说明其物质来源和富集条件有一定相似性,即陆源物质和海水共同影响的结果。稀土元素的分布模式以及∑REE与灰分、Si、Al的相关性说明了其主要来源于陆源物质;辰溪煤中δCe与δEu在剖面上变化很小,说明海水对煤中的稀土元素存在重新改造的作用。     

Rare earth element (REE) in surface mangrove sediment by instrumental neutron activation analysis

A study is carried out on the concentrations of rare earth element (REE) elements present in surface mangrove sediments from 10 locations throughout west coast Malaysia. In carrying out the analysis, the best and most convenient method being the instrumental neutron activation analysis (INAA). Samples were obtained, dried, crushed to powdery form and samples prepared for INAA. All the samples for analysis were weighted approximately 150 mg for short irradiation and 200 mg for long irradiation time. As calibration and quality control procedures, blank samples, standard reference material SL-1 were then irradiated with thermal neutron flux of 4 × 10¹² cm^?2 s^?1 at the MINT TRIGA Mark II research reactor which operated at 750 kW by using a pneumatic transport facility. The REE elements of surface sediment samples in this study are Dy, Sm, Eu,Yb, Lu, Tb, La and Ce. It was found that the level of concentrations of all the REE elements varies in the range (0.35–117.4 mg/kg). The geochemical behavior of REEs in surface sediments and normalized pattern (chondrite and shale) has been studied. The degree of sediments contaminations were computed using an enrichment factor. The results showed that the enrichment factor varied in the range (0.75–6.75).     

Complexes of Lanthanide Nitrates with Alkyl Esters of Bromomethylenediphosphonic Acid

Complexes of lanthanide nitrates (La, Ce, Sm, Gd, Er, and Yb) with tetraethyl and tetraisopropyl esters of bromomethylenediphosphonic acid were prepared. The complexes were characterized by elemental analysis, IR spectroscopy, and, in some cases, NMR. The data confirm that diphosphonates coordinate with two P[dbnd]O groups, and there are no indications for the existence of noncoordinated P[dbnd]O groups. The structure of the complexes depends only on the ionic radius of the central metal atom and not on changes in the electronic or steric behavior of the ester groups. For the complexes of La, Ce, Sm, and Gd nitrates, the formula is LnL₂(NO₃)₃, and for Er and Yb nitrates it is Ln₂L₃(NO₃)₆ (Ln[dbnd]La, Ce, Sm, Gd, Er, Yb; L = diphosphonate).     

The concentration of rare earth elements in plants and in the adjacent soils

La, Ce, Nd, Sm, Eu, Tb, Yb and Lu were determined in needles of age class 5 from 6 individual Norway spruce trees and in their soils. Measurements were done by neutron activation analysis with a group separation of the REE. Concentrations in spruce needles are among the lowest values reported for plant leaves. Concentrations show small variations between the soils, but large variations between the trees. The mean ratio plant/soil is about 5·10^–3 forall REE except Ce. Needles have no Eu-anomaly and a strong negative Ce-anomaly with respect to the soil. In addition to the fractionation of the individual REE between trees and the soil, there is also a considerable fractionation between the trees.     

Determination of the contents and distribution characteristics of REE in natural plants by NAA

The concentration of 8 REEs (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in 17 species of plants and their host soil, which were collected from a rare earth ore area located in the south of China, have been determined by INAA. The chondritic normalized REE patterns for different parts of plants (e.g., leaf stem and root) and their host soils were studied. The results showed that the concentration levels of REE for most plants in the sampling area were elevated. Particularly, the leaves of the fern (Dicranopteris dichotoma) contain extremely high concentration of the total REE (675–3358 g/g) Generally, these REE distribution patterns in every part of plants were very similar and reflected the characteristics of their host soils. However, the chondritic normalized REE patterns in some plants relative to the host soil revealed obvious fractionation, such as the depletion of the heavy REE (for fernCitrus reticulata andBrassia campestris), the heavy REE enrichment (forCamellia sinensis, Camellia oleifera andZiziphus) and the Ce positive anomaly (forGardenia jasminoides).     

Reduction specifics of rare-earth orthovanadates (REE = La,Nd, Sm,Dy, Ho,Er, Tm,Yb, and Lu)

The reduction specifics of REE orthovanadates LnVO₄ (Ln = La, Nd, Sm, Dy, Ho, Er, Tm, Yb, and Lu) have been studied using the temperature-programmed reduction (TPR) method. Hydrogen and carbon monoxide were chosen as reducing agents. The reduction temperature is found to depend both on the REE and the reducing agent. REE orthovanadates are reduced in the range 1033–1153 K not forming phases that contain vanadium in intermediate oxidation states. In CO, the reduction temperature is found to be higher than in H₂ for all orthovanadates. TPR data have been used to calculate the activation energies of reduction of REE orthovanadates using the Kissinger equation. The effective activation energies of reduction depend on the REE and the reducing agent and are in the range 41–147 kJ/mol.     

Inductively coupled plasma atomic emission spectroscopic determination of rare earth elements in geological samples after preconcentration by countercurrent chromatography—Part II

This paper directly links up with Part I [Spectrochim. Acta 48B, 1365 (1993)] which treats the first application of countercurrent chromatography (CCC) for pre-separation of rare earth elements (REE) in rocks. The rapid and reliable separation and pre-concentration of “light” REE and Y can be achieved using a system of 0.5 mol/l di-2-ethylhexylphosphoric acid (D2EHPA) in n-decane-hydrochloric acid of different concentrations and a planetary centrifuge as a CCC device. However, Tm, Yb and Lu are partially retained in the stationary phase. Comparative data is presented on three other two-phase liquid systems containing trioctylphosphine oxide (TOPO); D2EHPA and TOPO mixtures and diphenyl(dibutylcarbamoylmethylphosphine)oxide (Ph₂-Bu₂) as extractants in terms of their ability for whole REE group complete isolation from the rock constituents. The partial losses of “light” REE (La and Ce) occurred in the system of 0.1 mol/l solution of TOPO in isobutylmethylketone (IBMK) (stationary phase)-1 mol/l NH₄NO₃-6 mol/l HCl aqueous solutions (mobile phase). Complete isolution of the entire REE group can be reached in two systems: 0.3 mol/l D2EHPA + 0.02 ml/l TOPO in the solvents mixture (3:1) of n-decane + IBMK, respectively (stationary phase)-1 mol/l NH₄NO₃-6 mol/l HCl aqueous solution (mobile phase), and 1.0 mol/l Ph₂-Bu₂ solution in chloroform (stationary phase)-3 mol/l HNO₃ aqueous solution (mobile phase). The D2EHPA + TOPO mixture is recommended as more economic and accessible.     

Interactions of trivalent lanthanide cations with a hexadentate Schiff base derived from the condensation of ethylenediamine with 8-hydroxyquinoline-2-carboxaldehyde

Lanthanide(III) complexes [Ln(NO₃)₂(HL)] where Ln?=?La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb and Lu and LH₂?=?N,N′-bis(quinolin-8-ol-2-ylmethylidene)ethane-1,2-diamine, have been obtained by direct reaction of the di-Schiff base ligand and the corresponding hydrated lanthanide(III) nitrates in methanol/DMF solvent systems. All complexes were characterized with microanalyses, spectroscopically (IR and electronic spectra) and thermogravimetrically. Theoretical studies have also been undertaken to estimate possible structures. All the data are discussed in terms of the nature of the bonding and the possible structural types. All complexes appear to be monomeric with the organic ligand being singly deprotonated and behaving as a hexadentate chelating ligand.