THERMAL-DECOMPOSITION PROCESS OF SOME RARE-EARTH NITRILOTRIACETIC ACID SERINE MIXED COMPLEXES

Thermal decomposition processes of the mixed complexes of nitrilotriacetates of Pr, Sm, Tb, Ho and Tm with 2-amino-3-hydroxypropionic acid have been investigated. The results indicate that serine may coordinate to the rare earth ion via its hydroxyl group, not by means of its carboxyl group. From the thermogravimetric and the derivative thermogravimetric curves it can be deduced that there may be six or seven steps in the thermal decomposition process of these mixed complexes, and that not all thermal decomposition processes in these mixed complexes are the same. Some possible thermal decomposition reactions have been proposed, and the differences between the thermal decomposition processes of these complexes are also discussed.

A NEW HYDROGEN SENSOR WITH RARE-EARTH COMPLEX FLUORIDE

A new type of solid-state galvanic cell for detecting a small amount of hydrogen in air at room temperature is proposed. The sensor cell is a potentiometric cell using Ce0.95Ca0.05F2.95 as solid-state electrolyte. The cell exhibits good sensing properties to hydrogen in air at room temperature.

STUDY ON COMPLEXES OF RARE-EARTH WITH L-PHENYLALANINE BY POTENTIOMETRY WITH CALORIMETRY

The stability constants and thermodynamic functions for complexes of rare earth with L-phenylalanine have been determined by potentiometry and calorimetry at 25-degrees-C and ionic strength of 0.15mol.dm-3(NaCl). Stability of the complexes shows the "Tetrad effect". The entropy change makes a predominant contribution to the stability of these complexes. The ligand is coordinated to rare earth ions through its -CO2- and -NH2 group, and dehydration of ions plays an important role in coordination reaction.

INVESTIGATION OF THE PHOTOELECTRONIC PROPERTIES OF RARE-EARTH MONOPHOSPHIDES

The optical, electrical and photoelectronic properties of rare earth monophosphides (LnP, Ln = La, Nd, Sm and Y) have been studied. The experimental results indicate that their resistivities are low, the electric conduction in all of them is N-type, the energy gaps of LaP, NdP, SmP and YP are 1.46eV, 1.15eV, 1.1eV and 1.0eV, respectively. The SmP/Si and YP/Si junctions exhibit the photovoltaic effect. They may be used as photoelectronic sensors.

THE PHOTOELECTRIC PROPERTIES OF THIN-FILMS OF RARE-EARTH MONOPHOSPHIDES

The optical, electrical and photoelectric properties of rare earth monophosphides (LnP, Ln = La, Nd, Sm, Y, Dy and Yb) have been studied in thin films. The films exhibit semiconducting behaviour with energy gaps of 1.0-1.46 eV and n-type electrical conduction. Their resistivities are 10(-2) OMEGA-cm with corresponding Hall mobilities of 8.5-400 cm2 V-1 s-1. The films are deposited on a p-type silicon substrate in vacuum. Voltage-current characteristic measurements show that a p-n junction has been formed between LnP and silicon. Spectral sensitivity and a photovoltaic effect have been observed in LnP-Si junctions. They may be useful photoelectric materials.

COORDINATION CHEMISTRY AND SUPERCONDUCTIVITY

Analysing the coordination state of copper ions in cuprate superconductors, it is found that the larger the energy splitting between d(x2-y2) and d(z2) orbitals of Cu or the higher the energy of the d(x2-y2) orbital, the higher the Tc. Thus, appropriate coordination structures and strong-field ligands must be chosen for expanding the energy splitting and increasing the energy of the d(x2-y2) orbital when searching for new high-Tc superconductors. Summarizing the experimental results of ESR and XPS, it is considered that the [Cu2+ - O open-square-box 2- - Cu3+] resonance exists in cuprate superconductors and the electron field breathing mode is present. Analysing the mechanism and the relationship between the coordination state of Cu and Tc, we consider that the two dimensional Cu-O planes are responsible for the superconductivity of YBa2Cu3O7-y.

XPS STUDY ON RARE-EARTH PHTHALOCYANINE COMPLEXES

The rare earth monophthalocyanine complexes, LnPcCl and LnPc(OAc)2 (Ln = Tb, Ho, Tm, Lu, Pc=Phthalocyanine, OAc = Acetate), were synthesized. The electronic structures of the complexes have been studied by means of XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L-->Ln charge transfer. This L-->Ln charge transfer process of phythalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O1s binding energies of coordinating oxygen atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination number, valence state and so on. Because coordination number of Ln in LnPc(OAc)2 is larger than that in LnPcCl and electronegativity of Clin LnPcCl is larger than that of O in LnPc(OAc)2, the Ln4d5/2 binding energies of LnPc (OAc)2 are less than those of LnPcCl.

DIELS-ALDER REACTION CATALYZED BY RARE-EARTH CHLORIDES

Rare earth chlorides were used to catalyze the synthesis of 2-butoxy-3, 4-dihydro-2H-pyran using equimolar acrolein and vinyl butyl either. The cycloadduct is unstable which undergoes catalytic ring opening oligomerization. The way to stabilize the cyclo adduct has been studied, thus high yields of 90-95% were obtained.

Geochemistry of rare earth elements in cobalt-rich crusts from the Mid-Pacific M seamount

Rare earth elements (RFEs) and major elements of 25 cobalt-rich crusts obtained from different depths of Mid-Pacific M seamount were analyzed using inductively coupled plasma-atomic emission spectrometer and gravimetric method. The results showed that they were hydrogenous crusts with average Sigma REE content of 2084.69 mu g/g and the light REE (LREE)/heavy REE (HREE) ratio of 4.84. The shale-normalized PEE patterns showed positive Ce anomalies. The total content of strictly trivalent REEs increased with water depth. The Ce content and LREE/HREE ratios in Fe-Mn crusts above 2000 in were lower than those below 2000 m. The change in RE E with water depth could be explained by two processes: adsorptive scavenging by setting matters and behaviors of REE in seawater. However, the Ce abundance took no obvious correlation with water depth reflects the constant Ce flux. The Cc in crusts existed mainly as Ce(IV), implying that the oxidative-enriching process was controlled by kinetic factors.

Rare earth elements in bottom sediments of major rivers around the Yellow Sea: implications for sediment provenance

Rare earth elements (REEs) of 91 fine-grained bottom sediment samples from five major rivers in Korea (the Han, Keum, and Yeongsan) and China (the Changjiang and Huanghe) were studied to investigate their potential as source indicator for Yellow Sea shelf sediments, this being the first synthetic report on REE trends for bottom sediments of these rivers. The results show distinct differences in REE contents and their upper continental crust (UCC)-normalized patterns: compared to heavy rare earth elements (HREEs), light rare earth elements (LREEs) are highly enriched in Korean river sediments, in contrast to Chinese river sediments that have a characteristic positive Eu anomaly. This phenomenon is observed also in primary source rocks within the river catchments. This suggests that source rock composition is the primary control on the REE signatures of these river sediments, due largely to variations in the levels of chlorite and monazite, which are more abundant in Korean bottom river sediments. Systematic variations in I LREE pound/I HREE pound ratios, and in (La/Yb)-(Gd/Yb)(UCC) but also (La/Lu)-(La/Y)(UCC) and (La/Y)-(Gd/Lu)(UCC) relations have the greatest discriminatory power. These findings are consistent with, but considerably expand on the limited datasets available to date for suspended sediments. Evidently, the REE fingerprints of these river sediments can serve as a useful diagnostic tool for tracing the provenance of sediments in the Yellow Sea, and for reconstructing their dispersal patterns and the circulation system of the modern shelf, as well as the paleoenvironmental record of this and adjoining marginal seas.

Geochemical character and material source of sediments in the eastern Philippine Sea

Based upon analyses of grain-size, rare earth element (REE) compositions, elemental occurrence phases of REE, and U-series isotopic dating, the sediment characteristics and material sources of the study area were examined for the recently formed deep-sea clays in the eastern Philippine Sea. The analytical results are summarized as follows. (1) Low accumulation rate, poor sorting and roundness, and high contents of grains coarser than fine silt indicate relatively low sediment input, with localized material source without long distance transport. (2) The REE Contents are relatively high. Shale-normalized patterns of REE indicate weak enrichment in heavy REE (HREE), Ce-passive anomaly, and Eu-positive anomaly. (3) Elemental occurrence phases of REE between the sediments with and without crust are similar. REE mainly concentrate in residual phase and then in ferromanganese oxide phase. The light REE (LREE) enrichment, Ce-positive anomaly, and Eu-positive anomaly occur in residual phase. Ferromanganese oxide phase shows the characteristics of relatively high HREE content and Ce-passive anomaly. (4) There are differences in each above mentioned aspect between the sediments with and without ferromanganese crust. (5) Synthesizing the above characteristics and source discriminant analysis, the study sediments are deduced to mainly result from the alteration of local and nearby volcanic materials. Continental materials transported by wind and/or river (ocean) flows also have minor contributions.

Origin of a native sulfur chimney in the Kueishantao hydrothermal field, offshore northeast Taiwan

Analyses of rare earth and trace element concentrations of native sulfur samples from the Kueishantao hydrothermal field were performed at the Seafloor Hydrothermal Activity Laboratory of the Key Laboratory of Marine Geology and Environment, Institute of Oceanology, Chinese Academy of Sciences. Using an Elan DRC II ICP-MS, and combining the sulfur isotopic compositions of native sulfur samples, we studied the sources and formation of a native sulfur chimney. The results show, when comparing them with native sulfur from crater lakes and other volcanic areas, that the native sulfur content of this chimney is very high (99.96%), the rare earth element (REE) and trace element constituents of the chimney are very low (Sigma REE < 21x10(-9)), and the chondrite-normalized REE patterns of the native sulfur samples are similar to those of the Kueishantao andesite, implying that the interaction of subseafloor fluid-andesite at the Kueishantao hydrothermal field was of short duration. The sulfur isotopic compositions of the native sulfur samples reveal that the sulfur of the chimney, from H2S and SO2, originated by magmatic degassing and that the REEs and trace elements are mostly from the Kueishantao andesite and partly from seawater. Combining these results with an analysis of the thermodynamics, it is clear that from the relatively low temperature (< 116 degrees C), the oxygenated and acidic environment is favorable for formation of this native sulfur chimney in the Kueishantao hydrothermal field.

A preliminary study on fingerprinting approach in marine sediment dynamics with the rare earth elements

Locating the quantitized natural sediment fingerprints is an important work for marine sediment dynamics study. The total of 146 sediment samples were collected from the Shelf of the East China Sea and five rivers, including Huanghe (Yellow), Changjiang (Yangtze), Qiantang, Ou and Min River. The sediment grain size and the contents of rare earth elements (REEs) were measured with laser particle size analyzer and ICP-MS technology. The results show that absolute REE content (Sigma REE) and the concentration ratio of light REEs to heavy REEs (L/HREE) are different in the sediments among those rivers. There are higher REE contents in being less than 2 m and 2-31 mu m fractions in the Changjiang Estuary surface sediments. The REE contents of bulk sediment are dominated by the corresponding values of those leading size-fractions. Sigma REE of sediment is higher close to the estuaries and declines seaward on the inner shelf of the East China Sea (ECS). The L/HREE ratio has a tendency of increase southward from 28 degrees N. Hydrodynamic conditions plays a predominate role on spacial distributions of the surficial sediment's REE parameters. In some situations, the currents tend to remove the coarser light grains from initial populations, as well as the deposit of the finer heavy mineral grains. In other situations, the currents will change the ratio of sediment constituents, such as ratio between silts and clays in the sediments. As a result, the various values of Sigma REE or L/HREE ratio in different bulk sediments are more affected by the change of size-fractions than source location. Under the long-term stable hydrodynamic environment, i.e., the East China Sea Shelf, new sediment transport model based on the size and density gradation concept may help to understand the spatial distribution patterns of REE parameters.

内蒙古白云鄂博地区元古宙构造-岩浆演化史与超大型REE-Nb-Fe矿床成因

Bayan Obo giant REE-Nb-Fe deposit in the northen margin of the North China Craton (NCC) is well known in the world for its abundant rare earth element resources. There is nearly one hundred year of studying history in substance component, chronology and geochemistry of the ore deposit, since the main ore body was found in 1927. However, there still exist remarkable divergences in genesis, mineralized age and material origin. Especially the REE enrichment mechanism leaves us a secret. Recent research shows that the Bayan Obo ore deposit likely resulted from the carbonatite magma activity, which is a favorable factor for REE accumulation. Based on the analysis of tectonic evolution history of north margin of NCC this thesis mainly discussed the formation background of cratonic margined rifts in Bayan Obo, and presented the analytical results of formation environment, intrusion age and deep origin of Proterozoic carbonatite magma. These research results can provide evidence for ore genesis. LA ICP-MS U-Pb dating on zircon shows that the Neoarchean basement was mainly composed of calc-alkaline TTG gneisses (2588±16Ma). The collision orogeny movement of the northen margin of the NCC between 2.0 Ga to 1.9 Ga brought the swarm of diorite-granodiotite magma (2023±16Ma) and intense regional metamorphism event (1906.3±7.7 Ma to 1892.7±6.7 Ma). In the sequent super continent break up background, intense metamorphic and deformed basement complex was uplifted to the surface suffered denudation, forming Mesoproterozoic Bayan Obo group in the contemporary continental margin rifts. The uplift of basement complex and formation of continental rifts were likely related with mantle plume activity. Evidence from petrological and geochemical data suggests that abundant alkaline-basic magma resulted from enhancement of continental breakup activity, that separated into carbonatite veins and mafic dykes by melt immiscibility mechanism, intruded in Bayan Obo margin rifts at the late stage of extension movement. Carbonatite veins can be divided into three main types by mineral composition: dolomite carbonatite, dolomite-calcite coexistent carbonatite and calcite carbonatite. Intrusion relationship between different types of carbonatite veins show that the calcite carbonatite veins were formed latter than the dolomite type as well as the coexistent type. Moreover, geochemical data also reveals successive and evolutive character between them. The content of REE increases together with the calcite minerals component. That is to say that REE gradually accumulated as the evolution of carbonatite magma. High precision Sm-Nd isochron data shows that the intrusion age of carbonatite veins was at 1319±48Ma. Moreover, the REE mineralization age in calcite carbonatite veins was around 1275±87Ma that is consistent with the intrusion age in error range. According to these data the abundant REE already existed in the carbonatite magma before intrusion and result in the earlier ore mineralization. The average age of mineralized dolomite was at 1353±100Ma, and the mineralization age of apatite in coarse grain dolomite was around 1329±150Ma. These data is consistent with carbonatite. Considering the coincident rare, trace element and isochron composition between them, it is presumed that mineralized dolomite was also the carbonatite intrusion and was the mainly factor for huge REE enrichment.

山东平度大庄子金矿床地质地球化学特征及成因——兼论层间滑动角砾岩型金矿成矿模式

The author selected the geological and geochemical characteristics and the genesis of the Dazhuangzi gold deposit in the Pingdu City as the central content of the study. The author summarized geological features of the other gold deposits formed within the same geological setting along the margin of the Jiaolai pull-apart basin and compared these gold deposits with the Dazhuangzi gold deposit. On the basis of the first-hand data obtained from field investigation and from mining production reports, ore-controlling structures, geological characteristics and mineralization regularities of the Dazhuangzi gold deposit are studied in detail. According to the analyzing results of petrochemistry, trace element, rare earth element and fluid inclusion etc., the geochemical characteristics, the genesis and the ore-forming material source of the Dazhuangzi gold deposit and that of the other similar gold deposits along the margin of the Jiaolai Basin are proposed. The study results suggest that the Dazhuangzi gold deposit belongs to the typical interstratified glide breccia type gold deposit, which is controlled by the interstratified glide fault structure located along the margin of the Mesozoic pull-apart Jiaolai basin. The interstratified glide fault structure is in the outer part of unconformity belt between the overlying strata and the basement of the pull-apart basin, being along the marble strata of the Jingshan group. The formation of the ore-controlling structure is related closely with the evolution of the Jiaolai Basin in the Mesozoic. The ore-controlling structure underwent the structural stress changes from compressive to tensional and then to compressive stress with strike slipping features sequentially, which were coincided with the regional tectonic stress evolution. The interstratified glide breccia type gold mineralization mainly occurs in the siliceous-marble breccias and cataclastic rocks within the interstratified glide fault structure. The gold minerogenetic epoch is later than 120Ma when the ore-controlling structure was tensioning and strike-slipping. The occurrences of the ore controlling structure and the gold ore bodies are the same as that of the unconformity belt. The geological and geochemical studies show that the source of the ore-forming material is alike with that of the volcanic rocks of the Qingshan formation, which is widespread in the Jiaolai Basin. Both of them came from the deep crust or even the upper mantle. Based on the geological characteristics and the minerogenetic regularities of the Dazhuangzi gold deposit, a genetic model of the deposit is constructed. In addition, the author used the remote sensing image and exploration results of geochemical and geophysical methods to point out several prospecting areas for further exploration. Through comprehensive study on the interstratified glide fault structure and on the interstratified glide breccia type gold deposits along the Jiaolai pull-apart basin, three types of interstratified glide structures and related gold mineralization are set up according to evolution and distribution of main fault as well as related secondary faults in time and space. They are named as Penjiakuang type, Dazhuangzi type and Fayunkuang type. The author summarized up the minerogenetic characteristics and regularities controlled by these three different types of interstratified glide structures respectively, and set up a general minerogenetic model of the interstratified glide breccia type gold deposit.