INFRARED-SPECTRA OF DIMETHYLPHOSPHATE LANTHANIDE COMPLEXES

The infrared spectra of the crystalline solid samples of rare earth(III) dimethylphosphates Ln(DMP)3 (Ln = La, Ce, Nd) in the range 4000-100 cm-1 are discussed. It is shown that the spectra may be treated by dividing Ln(DMP)3 into two parts, an OP(OCH3)2O bridge and a LnO6 distortion octahedron. The absorption bands above 500 cm-1 may be clearly assigned. However, vibrational assignments in the far-infrared region are tentative.

AN INFRARED SPECTROSCOPIC STUDY ON THE STRUCTURAL PHASE-TRANSITIONS OF LAURYLAMMONIUM CHLORIDE

Infrared spectroscopy was used to study the structural phase, transitions of laurylammonium chloride in the temperature range from 290 to 365K. It was shown that there is a solid-solid phase transition at 339 K with a pre-transition at 327 K. The infrared spectra indicated that virgin crystals at room temperature form a well-ordered phase with all-trans hydrocarbon chains, and the lengths of N-H...Cl hydrogen bonds are different. The spectra suggested that the gauche conformers begin to appear at temperature above 327 K. The spectra at high temperature over 339 K demonstrated that the interaction between the chains decreases, the partial ''melting'' of the chains is obvious, and the hydrogen bonds (N-H...Cl) have the same lengths. The main transition and pre-transition are mainly assigned to the intramolecular and intermolecular order-disorder changes, respectively.

AN INFRARED SPECTROSCOPIC CHARACTERIZATION OF THE SOLID SOLID BEHAVIOR OF DODECYLAMMONIUM CHLORIDE

The infrared spectra of the bilayer system dodecylammonium chloride has been studied as a function of temperature. Unusual splitting of some vibrational modes helps us to characterize the structure of different solid states. This study provided the evidence for the occurrence of an order-disorder phase transition whose onset occurs at 327 K and its completion ends at 339 K. In the low temperature phase below 327 K, the virgin crystals form a well-ordered phase with all-transhydrocarbon chains. In the intermediate state between 327 and 339 K, the data demonstrate the introduction of intramolecular as well as intermolecular disorder. The coexistence of solid and liquid-crystal-like states is shown by the persistence of factor group splittings together with the existence of defect bands in the wide intermediate temperature range. In the high temperature phase over 339 K the crystals convert to a liquid-crystal-like system with extensive motional and conformational disorder, but still show characteristics in their infrared spectra which indicate the presence of ordered segments in the hexagonal solid phase.

AN INFRARED SPECTROSCOPIC STUDY OF THE STRUCTURAL PHASE-TRANSITION IN THE PEROVSKITE-TYPE LAYER COMPOUND [N-C16H33NH3]2COCL4

The solid-solid phase transitions in the perovskite-type layer compound [n- C16H33NH3]2CoCl4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.

INFRARED SPECTRA AND CRYSTAL STRUCTURE OF BIS-(DIMETHOXYLPHOSPHATO) COPPER

The title complex has beep synthesized by the reaction of CaCl2, with trimethyl phosphate. Its Infrared spectra from 4000 to 100 cm(-1) measured. The assignment of acme absorption bands was discussed. It is found that the stretching vibrations of bridge groups O-P-O are divided into two groups according to their bond length. The crystal structure of the complex boa been determined from single crystal K-ray diffraction data. The crystals belong to monoclinic system, space group P2(1)/c with cell parameteras, a = 1,0704(4), b = 0.5093(2), c = 1.9737(6)nm, beta = 96.23(3)degrees, V = 1.0696(6)nm(2), Z = 4, final R = 0.044. Copper ion is coordinated to five Rimester oxygen atoms to form a distorted square pyramid. The adjacent copper ions are connected by symmetric and non-symmetric bridge groups of O-P-O, forming an infinite one-dimensional chain coordination polymer.

THERMAL ANALYSIS AND INFRARED SPECTRA OF DIALKYLAMMONIUM TETRAC HLOROCUPRATE

The thermal stability and the solid solid phase transitions in Ills compounds with n = 7-12 have been studied by DSC and TG methods. Comparision with CnZn compounds want made. The nature of three phases of CnCu has been discussed in terms of infrared spectroscopy and the assignment of the phase transitions has been given. The thermal stability of CnCu is lower than that of CnZn and presents an obvious odd even effect. All of these compounds exhibit two solid solid phase transitions in the temperature range of 248-337 K. The peak tempe nature of phase transitions changes regularly. The peak temperature or the main phase transition increases with the chain length. The total transition enthalpies and entropies increase with increasing chain length. When n <= 9, the high temperature phase exists in a partial disorder state. When n >= 10, the high temperature phase exists in a conformational disorder state. The main phase transition and the phase transition at 307.7 K of CnCu may mainly are from the change of the packing structure and the change of the partial conformational order-disorder of alkyl chain, respectively.

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.

Sedimentation rates and provenance analysis in the Southwestern Okinawa Trough since the mid-Holocene

As a high-sedimentation rate depocenter along the path of the Kuroshio Current, the southwesternmost part of the Okinawa Trough is a key area to understand the Kuroshio history and sediments transportation. A 34.17-m-long sediment core was obtained by the advanced piston corer of Marco Polo/IMAGES XII MARION DUFRESNE during the May 2005 from the Southern Okinawa Trough at site MD05-2908. The recovered sediments were analyzed by AMS C-14 dating, coarse size fraction (> 63 mu m) extraction and moisture content determination in order to study its sedimentation flux and provenance. The depth-age relationship of core MD05-2908 was well constrained by 17 C-14 dating points. The sediments span across the mid-Holocene (6.8 ka B.P.) and have remarkablely high sedimentation rates between 1.8 and 21-2 m/ka, which is well consistent with the modern observations from sediment traps. We identified five 70-200 a periods of abnormally rapid sedimentation events at 6790-6600 a B.P., 5690-5600 a B.P., 4820-4720 a B.P., 1090-880 a B.P., and 260-190 a B.P., during which the highest sedimentation rate is up to 21-2 m/ka. In general, the lithology of the sediments were dominated by silt and clay, associated with less than 5% coarse size fraction (a parts per thousand << 63 mu m). As the most significant sediment source, the Lanyang River in northeastern Taiwan annually deliver about 10Mt materials to the coastal and offshore region of northeast Taiwan, a portion of which could be carried northward by currents toward the study area. Therefore, we concluded that the 5 abnormally rapid sedimentation events may be related to intensified rainfall in Taiwan and thus increased materials to our study area at that time. However, a few extreme-rapid sedimentation events cannot be explained by normal river runoff alone. The large earthquakes or typhoons induced hyperpycnal discharge of fluvial sediment to the ocean may also act as a potential source supply to the Okinawa Trough.

He, Ne and Ar isotope compositions of fluid inclusions in hydrothermal sulfides from the TAG hydrothermal field, Mid-Atlantic Ridge

Helium, rieon and argon isotope compositions of fluid inclusions have been measured in hydrothermal sulfide samples from the TAG hydrothermal field at the Mid-Atlantic Ridge. Fluid-inclusion He-3/He-4 ratios are 2.2-13.3 times the air value (Ra), and with a mean of 7.2 Ra. Comparison with the local vent fluids (He-3/He-4=7.5-8.2 Ra) and mid-ocean ridge basalt values (He-3/He-4=6-11 Ra) shows that the variation range of He-3/He-4 ratios from sulfide-hosted fluid inclusions is significantly large. Values for Ne-20/Ne-22 are from 10.2 to 11.4, which are significantly higher than the atmospheric ratio (9.8). And fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 359, which are close to the atmospheric values (295.5). These results indicate that the noble gases of fluid inclusions in hydrothermal sulfides are a mixture of mantle- and seawater-derived noble gases; the partial mantle-derived components of trapped hydrothermal fluids may be from the lower mantle; the helium of fluid inclusions is mainly from upper mantle; and the Ne and Ar components are mainly from seawater.

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

Records of the East Asian winter monsoon from the mud area on the inner shelf of the East China Sea since the mid-Holocene

AMS(14)C dating and analysis of grain size, major elements and clay minerals were applied to Core MZ01 from the mud area on the inner shelf of the East China Sea. Based on the environmentally sensitive grain size, clay mineral and major element assemblages, the history of the East Asia winter monsoon since the mid-Holocene could be reconstructed. These three proxies, mean grain size (>9.71 mu m), chemical index of alteration (CIA) and ratio of smectite to kaolinite in particular, show similar fluctuation patterns. Furthermore, 10 extreme values corresponding to the contemporary cooling events could be recognized since the mid-Holocene; these extreme values are likely to have been caused by the strengthening of the East Asia winter monsoon. The cooling events correlated well with the results of the delta O-18 curves of the Dunde ice core and GISP2, which therefore revealed a regional response to global climate change. Four stages of the East Asia winter monsoon were identified, i.e. 8300-6300 a BP, strong and unstable; 6300-3800 a BP, strong but stable; 3800-1400 a BP, weak and unstable; after 1400 a BP, weak but stable.