The thermal cycling behavior of Lanthanum-Cerium Oxide thermal barrier coating prepared by EB-PVD

Bulk material and coatings of Lanthanum-Cerium Oxide (La2Ce2O7) with a fluorite structure were studied as a candidate material for thermal barrier coating (TBC). It has been showed that such material has the properties of low thermal conductivity about four times lower than YSZ, the difference in the thermal expansion coefficient between La2Ce2O7 and bond coat is smaller than that of YSZ in TBC systems, high phase stability between room temperature and 1673 K, about 300 K higher than that of the YSZ. The coating prepared by electron beam physical vapor deposition (EB-PVD) showed that it has good thermal cycling behavior, implying that Such material can be a promising thermal barrier coating material. The deviation of coating composition from ingot can be overcome by the addition of excess La2O3 during ingot preparation and/or by adjusting the process parameters.

Effect of rare earth element on the metabolism in rats by high resolution proton nuclear magnetic resonance spectroscopy

The high-field nuclear magnetic resonance (NMR) spectra can be used for the rapid multicomponent analysis in small amounts of biological fluids. In this paper, the effect of La (NO3)(3) on the rats' metabolism in urine was investigated by H-1 NMR analysis. The experimental groups of wistar rats were injected intraperitoneally with La(NO3)(3) at doses of 0.2, 2.0, 10 and 20mg/kg body weight. The remarkable variation of low molecular weight metabolites in urine has been identified by H-1 NMR spectra, in which dimethylamine, N, N-dimethylglycine, urea, alpha -ketoglutarate, trimethylamine N-oxide, succinate, citrate and amino acids have been suggested as NMR markers for renal damage and ethanol, lactate, taurine as the markers for liver damage. This work may assess its possible use in the early detection of biochemical changes associated with Rare Earth induced kidney and liver dysfunction.

Synthesis, characterization and catalytic activity for H2O2 decomposition of tetrabasic tungstovanadophosphate heteropoly rare earth element complexes with Dawson structure

Nine tetrabasic tungstovanadophosphate heteropoly rare earth element complexes with Dawson structure were synthesized. Their general molecular formulas are K15H4[Ln . (P2W16VO61)(2)] . xH(2)O(Ln = La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, Yb3+). Their structures and properties were investigated by IR, UV, NMR, ESR, XRD, TG-DTA. The results showed that the series of complexes have the same structure as K-16[Ce(P2W17O61)(2)] . 50H(2)O. At the same time, the catalytic activity of the complexes for H2O2-decomposition was also investigated.

The direct electrochemistry of cytochrome c at the nanometer-sized rare earth element oxide particle-modified gold electrodes

The direct electrochemistry of cytochrome c was studied at nanometer-sized rare earth element dioxide particle-modified gold electrodes. It was demonstrated that rare earth element oxides can accelerate the electrochemical reaction of cytochrome c and the reversibility of the electrochemical reaction of cytochrome c was related to the size of rare earth element oxide particles.

ELECTROOXIDATION OF A CHLORIDE COMPLEX OF PLATINUM(II) AT A GLASSY-CARBON ELECTRODE

The electro-oxidation of PtCl42- was studied on a glassy carbon (GC) electrode. A Pt(IV) complex was formed on the electrode surface through coordination to the oxygen atom of an oxide functional group on the electrode, which results in its deactivation. The ferri/ferrocyanide redox couple was used as a probe to examine the activity of the GC electrode. X-ray photoelectron spectroscopy was employed to characterize the platinum on the electrode surface, and showed that the oxidation state of the Pt element changes depending on the electrochemical treatment of GC electrode. The platinum complex on the surface of the GC electrode can be transformed to Pt-0 by cycling the electrode between -0.25 and +1.65 V/SCE in 0.1 M H2SO4 solution. The above procedure can be used to disperse platinum ultramicroparticles on the surface of a GC electrode.

Extracellular hydrolytic enzyme screening of culturable heterotrophic bacteria from deep-sea sediments of the Southern Okinawa Trough

The Southern Okinawa Trough is an area of focused sedimentation due to particulate matter export from the shelf of the East China Sea and the island of Taiwan. In order to understand the geomicrobiological characteristics of this unique sedimentary environment, bacterial cultivations were carried out for an 8.61 m CASQ core sediment sample. A total of 98 heterotrophic bacterial isolates were characterized based on 16S rRNA gene phylogenetic analysis. These isolates can be grouped into four bacterial divisions, including 13 genera and more than 20 species. Bacteria of the gamma-Proteobacteria lineage, especially those from the Halomonas ( 27 isolates) and Psychrobacter ( 20 isolates) groups, dominate in the culturable bacteria assemblage. They also have the broadest distribution along the depth of the sediment. More than 72.4% of the isolates showed extracellular hydrolytic enzyme activities, such as amylases, proteases, lipases and Dnases, and nearly 59.2% were cold-adapted exoenzyme-producers. Several Halomonas strains show almost all the tested hydrolases activities. The wide distribution of exoenzyme activities in the isolates may indicate their important ecological role of element biogeochemical cycling in the studied deep-sea sedimentary environment.

Trace element composition of peridotites from the southern Mariana forearc: Insights into the geochemical effects of serpentinization and/or seafloor weathering

Peridotites from the southern Mariana forearc were sampled on the landward trench slope of the Izu-Bonin-Mariana (IBM) subduction zone by dredging. These mantle wedge peridotites underwent hydration by fluid derived from a dehydrated descending slab, and later interacted with seawater after emplacement at or near the seafloor. This study investigates how these two different rock-fluid interaction processes influenced trace element distribution in the southern Mariana forearc peridotites. We measured trace element concentrations of peridotites from the southern Mariana forearc. The southern Mariana forearc peridotites are characterized by a distinct seawater-like REE pattern with an obvious negative Ce anomaly, and La shows good correlation with other REEs (except Ce). In addition, there is a great enrichment of U, Pb, Sr and Li elements, which show a distinct positive anomaly relative to adjacent elements in the multi-element diagram. For the seawater-like REE pattern, we infer that REEs are mainly influenced by seawater during peridotite-seawater interactions after their emplacement at or near the seafloor, by serpentinization or by marine weathering. Furthermore, the anomalous behavior of Ce, compared with other rare earth elements in these samples, may indicate that they have undergone reactions involving Ce (IV) when the peridotites interacted with seawater. Positive U, Pb, Sr and Li anomalies are inferred to be related to seawater and/or fluids released during dehydration of the subducting slab.

Element enrichment and U-series isotopic characteristics of the hydrothermal sulfides at Jade site in the Okinawa Trough

The geochemical and U-series isotopic characteristics of hydrothermal sulfide samples from the Jade site (127A degrees 04.5'E, 27A degrees 15'N, water depth 1300-1450 m) at Jade site in the Okinawa Trough were analyzed. In the hydrothermal sulfide samples bearing sulfate (samples HOK1 and HOK2), the LREEs are relatively enriched. All the hydrothermal sulfide samples except HOK1 belong to Zn-rich hydrothermal sulfide. In comparison with Zn-rich hydrothermal sulfides from other fields, the contents of Zn, Pb, Ag, Cd, Au and Hg are higher, the contents of Fe, Al, Cr, Co, Ni, Sr, Te, Cs, Ti and U lower, and the Pb-210 radioactivity ratios and Pb-210/Pb ratios very low. In the hydrothermal sulfide mainly composed of sphalerite, the correlations between rare elements Hf and U, and Hf and Mn as well as that between dispersive elements Ga and Zn, are strongly positive; also the contents of Au and Ag are related to Fe-sulfide, because the low temperature promotes enrichment of Au and Ag. Meanwhile, the positive correlations between Fe and Bi and between Zn and Cd are not affected by the change of mineral assemblage. Based on the Pb-210/Pb ratios of hydrothermal sulfide samples (3.99x10(-5)-5.42x10(-5)), their U isotopic composition (U-238 content 1.15-2.53 ppm, U-238 activity 1.07-1.87 dpm/g, U-234 activity 1.15-2.09 dpm/g and U-234/U-238 ratio 1.07-1.14) and their Th-232 and Th-230 contents are at base level, and the chronological age of hydrothermal sulfide at Jade site in the Okinawa Trough is between 200 and 2000 yr.

Metasomatism of the peridotites from southern Mariana fore-arc: Trace element characteristics of clinopyroxene and amphibole

Modal composition and mineral composition of harzburgites from the southern Mariana fore-arc show that they are highly refractory. There are a few modals of clinopyroxene (0.7 vol %) in harzburgites. Two types of amphibole are found in these harzburgites: magnesiohornblende accompanied by clinopyroxene with higher Al2O3 content (> 7%) and lower Mg-#; tremolite around orthopyroxene with lower Al2O3 content (< 2%) and higher Mg-#. Trace element of clinopyroxene and two types of amphibole are analyzed. Primitive mantle-normalised REE patterns for clinopyroxene and magnesio hornblende are very similar and both show HREE enrichment relative to LREE, while magnesiohornblende has higher content of trace element than clinopyroxene. The contents of trace element of tremolite are much lower than those of magnesiohornblende. Clinopyroxene shows enrichment of most of the trace element except HREE and Ti relative to clinopyroxene in abyssal peridotites. Petrology and trace element characteristic of clinopyroxene and two types of amphibole indicate that southern Mariana fore-arc harzburgites underwent two stages of metasomatism. The percolation of a hydrous melt led to mobility of Al, Ca, Fe, Mg, Na, and large amounts of trace element. LILE and LREE can be more active in hydrous melt than HREE and Ti, and the activities of most of the trace element except some of LILE are influenced by temperature and pressure.

Major element, trace element, and Sr, Nd and Pb isotope studies of Cenozoic basalts from the South China Sea

The whole rock K-Ar ages of basalts from the South China Sea basin vary from 3.8 to 7.9 Ma, which suggest that intra-plate volcanism after the cessation of spreading of the South China Sea (SCS) is comparable to that in adjacent regions around the SCS, i.e., Leiqiong Peninsula, northern margin of the SCS, Indochina block, and so on. Based on detailed petrographic studies, we selected many fresh basaltic rocks and measured their major element, trace element, and Sr-Nd-Pb isotope compositions. Geochemical characteristics of major element and trace element show that these basaltic rocks belong to alkali basalt magma series, and are similar to OIB-type basalt. The extent of partial melting of mantle rock in source region is very low, and magma may experience crystallization differentiation and cumulation during the ascent to or storing in the high-level magma chamber. Sr-Nd-Pb isotopic data of these basaltic rocks imply an inhomogeneous mantle below the South China Sea. The nature of magma origin has a two end-member mixing model, one is EM2 (Enriched Mantle 2) which may be originated from mantle plume, the other is DMM (Depleted MORB Mantle). Pb isotopic characteristics show the Dupal anomaly in the South China Sea, and combined with newly found Dupal anomaly at Gakkel ridge in Arctic Ocean, this implies that Dupal anomaly is not only limited to South Hemisphere. In variation diagrams among Sr, Nd and Pb, the origin nature of mantle below the SCS is similar to those below Leiqiong peninsula, northern margin of the SCS and Indochina peninsula, and is different from those below north and northeast China. This study provides geochemical constraints on Hainan mantle plume.

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.

Boundary Element Method (BEM) Analysis for Galvanic Corrosion of Hot Dip Galvanized Steel Immersed in Seawater

A numerical analysis of galvanic corrosion of hot-dip galvanized steel immersed in seawater was presented. The analysis was based on the boundary element methods (BEMs) coupled with Newton-Raphson iterative technique to treat the nonlinear boundary conditions, which were determined by the experimental polarization curves. Results showed that galvanic current density concentrates on the boundary of steel substrate and zinc coating, and the sacrificial protection of zinc coating to steel substrate results in overprotection of steel cathode. Not only oxygen reduction but also hydrogen reduction could occur as cathode reactions, which probably led up to the adsorption and absorption of hydrogen atoms. Flat galvanized steel tensile sample shows a brittle behavior similar to hydrogen embrittlement according to the SSRT (show strain rate test) in seawater.

二氧化碳在孔隙咸水层中多相流动数值模拟研究

There has been a growing concern about the use of fossil fuels and its adverse effects on the atmospheric greenhouse and ecological environment. A reduction in the release rate of CO2 into the atmosphere poses a major challenge to the land ecology of China. The most promising way of achieving CO2 reduction is to dispose of CO2 in deep saline aquifers. Deep aquifers have a large potential for CO2 sequestration in geological medium in terms of volume and duration. Through the numerical simulation of multiphase flow in a porous media, the transformation and motion of CO2 in saline aquifers has been implemented under various temperature and hydrostatic pressure conditions, which plays an important role to the assessment of the reliability and safety of CO2 geological storage. As expected, the calculated results can provide meaningful and scientific information for management purposes. The key problem to the numerical simulation of multiphase flow in a porous media is to accurately capture the mass interface and to deal with the geological heterogeneity. In this study, the updated CE/SE (Space and time conservation element and solution element) method has been proposed, and the Hybrid Particle Level Set method (HPLS) has extended for multiphase flows in porous medium, which can accurately trace the transformation of the mass interface. The benchmark problems have been applied to evaluate and validate the proposed method. In this study, the reliability of CO2 storage in saline aquifers in Daqingzi oil field in Sunlong basin has been discussed. The simulation code developed in this study takes into account the state for CO2 covering the triple point temperature and pressure to the supercritical region. The geological heterogeneity has been implemented, using the well known geostatistical model (GSLIB) on the base of the hard data. The 2D and 3D model have been set up to simulate the CO2 multiphase flow in the porous saline aquifer, applying the CE/SE method and the HPLS method .The main contents and results are summarized as followings. (1) The 2D CE/SE method with first and second –order accuracy has been extended to simulate the multiphase flow in porous medium, which takes into account the contribution of source and sink in the momentum equation. The 3D CE/SE method with the first accuracy has been deduced. The accuracy and efficiency of the proposed CE/SE method have been investigated, using the benchmark problems. (2) The hybrid particle level set method has been made appropriate and extended for capturing the mass interface of multiphase flows in porous media, and the numerical method for level set function calculated has been formulated. (3) The closed equations for multiphase flow in porous medium has been developed, adept to both the Darcy flow and non-Darcy flow, getting over the limitation of Reynolds number to the calculation. It is found that Darcy number has a decisive influence on pressure as well as velocity given the Darcy number. (4) The new Euler scheme for numerical simulations of multiphase flows in porous medium has been proposed, which is efficient and can accurately capture the mass interface. The artificial compressibility method has been used to couple the velocities and pressure. It is found that the Darcy number has determinant effects on the numerical convergence and stability. In terms of the different Darcy numbers, the coefficient of artificial compressibility and the time step have been obtained. (5) The time scale of the critical instability for critical CO2 in the saline aquifer has been found, which is comparable with that of completely CO2 dissolved saline aquifer. (6) The concept model for CO2 multiphase flows in the saline aquifer has been configured, based on the temperature, pressure, porosity as well as permeability of the field site .Numerical simulation of CO2 hydrodynamic trapping in saline aquifers has been performed, applying the proposed CE/SE method. The state for CO2 has been employed to take into account realistic reservoir conditions for CO2 geological sequestration. The geological heterogeneity has been sufficiently treated , using the geostatistical model. (7) It is found that the Rayleigh-Taylor instability phenomenon, which is associated with the penetration of saline fluid into CO2 fluid in the direction of gravity, has been observed in CO2 multiphase flows in the saline aquifer. Development of a mushroom-type spike is a strong indication of the formation of Kelvin-Helmholtz instability due to the developed short wavelength perturbations present along the interface and parallel to the bulk flow. Additional key findings: the geological heterogeneity can distort the flow convection. The ascending of CO2 can induce the persistent flow cycling effects. The results show that boundary conditions of the field site have determinant effects on the transformation and motion of CO2 in saline aquifers. It is confirmed that the proposed method and numerical model has the reliability to simulate the process of the hydrodynamic trapping, which is the controlling mechanism for the initial period of CO2 storage at time scale of 100 years.

泥河湾盆地大长梁剖面岩石磁学和环境磁学研究

The fluvio-lacustrine sequence in the Nihewan Basin is an important archive of late Pliocene-Pleistocene climate and environment changes in temperate northern China, which provides excellent sources of early human settlements in high latitude East Asia. The recent years have witnessed a considerable progress in the paleomagnetic dating of its stratigraphy, which has notably increased our understanding of a series of important issues such as the early human occupation in the Old World, the infilling history of the Nihewan Basin, and the chronological sequence of the Nihewan faunas. Up to now, the long-term paleoenvironmental changes directly retrieved from this basin, which might influence the evolution and expansion of early humans in the Nihewan Basin, are still poorly constrained, although several paleoclimatic records have been retrieved from this area. In this study, a combined mineral-magnetic and geochemical investigation was carried out on the fluvio-lacustrine sequence from the Dachangliang section at the eastern margin of the basin in order to reveal its rock magnetic and environmental magnetic characteristics and its implications for early human evolution in East Asia. The major findings and conclusions are listed as the following: First, there is an increased cooling coupled with an intensified aridification recorded in the fluvio-lacustrine sequence of the Dachangliang section. The cooling is related to an up-section decrease in propensity to chemical weathering as inferred from an increase in low-field susceptibility after cycling to 700 °C. Close to 700 °C, reacting chlorite is providing the iron source for newly formed very fine-grained ferrimagnetic minerals which enhances the susceptibility signal. The reactivity of chlorite after annealing at temperatures above 600 °C is documented with X-ray diffraction. Second, degrees of chemical weathering in the Nihewan Basin are further estimated by clay mineralogy (i.e. chlorite and illite contents and chlorite/illite ratio) and a series of major element proxies (i.e. Na2O/Al2O3 versus K2O/Al2O3 diagram, Al2O3-(CaO + Na2O)-K2O ternary diagram (A-CN-K), chemical index of alteration (CIA), (CaO + Na2O + MgO)/TiO2, (CaO + Na2O + MgO + K2O)/(TiO2 + Al2O3), CaO/Al2O3 and CaO/TiO2). The up-section decrease in propensity to chemical weathering suggested by the aforementioned rock mangetic measurement is further confirmed by these geochemical analyses. Combining the chemical weathering records from the Nihewan Basin, Chinese Loess Plateau, South China Sea and eastern China, we find that the consecutive decreasing trend in chemical weathering intensity during the late Cenozoic is ubiquitous across China. This pattern may result from a long-term decreasing East Asian summer monsoon and increasing East Asian winter monsoon, and thus a consecutive increasing of aridification and cooling in Asia during the Quaternary. Furthermore, the chemical weathering intensity increased from South China to North China during the Quaternary, in line with the decreasing East Asian summer monsoon and increasing East Asian winter monsoon and thus the gradually intensified aridification and cooling from South China to North China. Third, a combined mineral-magnetic and geochemical investigation provides evidences that the large-amplitude alterations of concentration of magnetic minerals mainly result from preservation/dissolution cycles of detrital magnetic minerals in alternately oxic and anoxic depositional environments. The preservation/dissolution model implies that the high-magnetic and low-magnetic cycles of this sedimentary sequence represent glacial and interglacial climate cycles, respectively. This contribute significnatly to our understanding of the link between climate and magnetic properties. Finally, the paleoclimatic implications of these rock magnetic and geochemical characteristics significantly increase our understanding of the general setting of early humans in high northern latitude in East Asia. We propose that the cold and dry climate may have contributed significantly to the expansion and adaptation of early humans, rather than bringing hardship, as is often thought. The relationship between magnetic properties and climate possibly provides valuable information on the climatic context of the Paleolithic sites in the basin, especially whether the occupation occurred during an interglacial or glacial period.