SYNTHESES AND CRYSTAL-STRUCTURES OF TRIINDENYLLANTHANIDE COMPLEXES (ETA-5-C9H7)3LN.OC4H8 (LN=ND,GD,ER)

The complexes named in the title (eta-5-C9H7)3Ln.OC4H8 (Ln = Nd, Gd, Er) were synthesized by the reaction of anhydrous lanthanide trichlorides with indenyl potassium and cyclooctadienyl potassium (1:2:1 molar ratio) in THF. The complexes were characterized by elemental analysis, infrared and H-1-NMR spectroscopy, and mass spectrometry. In addition, the crystal structures of (eta-5-C9H7)3Nd.OC4H8 (1) and (eta-5-C9H7)3Gd.OC4H8 (2) were determined by an X-ray diffraction study. Complexes 1 and 2 belong to hexagonal space group P6(3) with unit cell parameters a = b = 11.843(3), c = 10.304(4) angstrom, V = 1251.7(9) angstrom-3, D(c) = 1.49 g.cm-3, Z = 2 for 1, and a = b = 11.805(2), c = 10.236(2) angstrom, V = 1235.4(6) angstrom-3 D(c) = 1.54 g.cm-3, Z = 2 for 2. The structures were solved by Patterson and Fourier techniques and refined by least-squares to final discrepancy indices of R = 0.049, R(w) = 0.053 using 925 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 1, and R = 0.023, R(w) = 0.025 using 1327 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 2. Coordination numbers for Nd3+ and Gd3+ are 10; the average bond lengths Nd-O and Gd-O are 2.557(21) and 2.459(13) angstrom, respectively. The structural studies showed the complexes to have 3-fold symmetry, but the THF molecule has no such symmetry; consequently the arrangement of carbon atoms in the THF molecule are disordered.

Antioxidative principals of Jussiaea repens: an edible medicinal plant

Jussiaea repens L. (JRL) is an edible medicinal plant and is also used as a vegetable by the local people in southwestern China. The crude extract and its four fractions derived from JRL were evaluated for the 1,1-diphenyl-2-picrylhydrazyl radical-scavenging ability, hydroxyl radical-scavenging capacity and the potassium ferricyanide reduction property. The ethyl acetate-soluble fraction (EAF) and EAF6 (a subfraction derived from EAF) were the most valuable fraction and subfraction, respectively. Furthermore, bioactivity-guided chromatographic fractionation revealed that three pure compounds greatly contributed to the antioxidant activities. Qualitative and quantitative analyses of the major antioxidant constituents in the extract were systematically conducted by NMR, mass spectral analyses and RP-HPLC. The result demonstrated that rosmarinic acid (2.00 mg g(-1) JRL dry weight) quercetin 3-O-beta-D-glucopyranoside (9.88 mg g(-1) JRL dry weight), and kaempferol 3-O-beta-D-glucopyranoside (1.85 mg g(-1) JRL dry weight) were the major antioxidative constituents in JRL. These compounds are reported for the first time from this plant.

Evaluation of antioxidant property of extract and fractions obtained from a red alga, Polysiphonia urceolata

Antioxidant activity (AA), total phenolic content, and reducing power of the crude extract, fractions, and subfractions derived from a red alga, Polysiphonia urceolata, were evaluated and determined. The antioxidative activity was measured using the alpha,alpha-diphenyl-beta-pierylhydrazyl (DPPH) radical scavenging assay and the P-carotene-linoleate assay systems, and compared with that of butylated hydroxytoluene (BHT), gallic acid (GA), and ascorbic acid (AscA). The results showed that the crude extract and the ethyl acetate-soluble fraction exhibited higher AA than BHT in the DPPH assay model, at all of four concentration levels tested (from 0.4 to 50 mu g/ml), while, in the beta-carotene-linoleate assay system, the crude extract and the ethyl acetate-soluble fraction exhibited similar or, in most cases, higher AA than GA and AscA at the same concentrations (from 10 to 200 mu g/ml). The ethyl acetate-soluble fraction was further fractionated into seven subfractions F1-F7 by silica gel vacuum liquid chromatography. F1 was found to be the most effective subfraction in both assay systems. The total phenolic content and reducing power were determined using the Folin-Ciocalteu and the potassium ferricyanide reduction methods, respectively. Statistical analysis indicated a significant association between the antioxidant potency and total phenolic content as well as between the antioxidant potency and reducing power. (c) 2005 Elsevier Ltd. All rights reserved.

Flow cytometry and ultrastructure of cryopreserved red seabream (Pagrus major) sperm

The objectives were to assess motility, fertilizing capacity, structural integrity, and mitochondrial function in fresh versus frozen-thawed (15% DMSO was used as a cryoprotectant) sperm from red seabrearn (Pagrus major). Mean (+/- S.D.) rates of motility, fertilization and hatching of frozen-thawed sperm were 81.0 +/- 5.4, 92.8 +/- 1.9, and 91.8 +/- 5.2%, respectively; for fresh sperm, they were 87.5 +/- 7.7, 95.8 +/- 2.4, and 93.8 +/- 4.2%. Although motility was lower in frozen-thawed versus fresh sperm (P < 0.05), there was no effect (P > 0.05) of cryopreservation on fertilization or hatching. Based on scanning and transmission electron microscopy, 77.8 +/- 5.6% of fresh sperm had normal morphology, whereas for frozen-thawed sperm, 63.0 +/- 7.2% had normal morphology, 20.6 +/- 3.1% were slightly damaged (e.g. swelling or rupture of head, mid-piece and tail region as well as mitochondria), and 16.4 +/- 4.2% were severely damaged. Sperm were stained with propidium iodide and Rhodamine 123 to assess plasma membrane integrity and mitochondrial function, respectively, and examined with flow cytometry. For fresh sperm, 83.9% had an intact membrane and functional mitochondria, whereas for frozen-thawed sperm, 74.8% had an intact membrane and functional mitochondria, 12.7% had a damaged membrane, 9.9% had nonfunctional mitochondria, and 2.6% had both a damaged membrane and nonfunctional mitochondria. In conclusion, ultrastructure and flow cytometry were valuable for assessment of frozen-thawed sperm quality; cryopreservation damaged the sperm but fertilizing ability was not significantly decreased. (c) 2007 Elsevier Inc. All rights reserved.

Use of computer-assisted sperm analysis (CASA) to evaluate the quality of cryopreserved sperm in red seabream (Pagrus major)

In the present study, the quality of post-thaw sperm of red seabream Pagrus major frozen with 6-24% DMSO was investigated. The motility, average path velocity and fertilizing capacity of fresh and their corresponding post-thaw sperm were examined for evaluation of the post-thaw sperm motion characteristics and its association with fertilizing capacity. An analysis of sperm motility before and after cryopreservation has been performed using computer-assisted sperm analysis (CASA). For post-thaw sperm frozen with 12-21% DMSO, the percentages of motile sperm were not significantly (P > 0.05) changed 10 s after activation. Moreover, the main motility pattern and swimming velocity of the motile post-thaw sperm were not significantly (P > 0.05) changed and the progressive linear motion was still the dominant pattern. However, the total motility of post-thaw sperm (72.3 +/- 6.3%) 30 s after activation was (P < 0.05) lower than the corresponding fresh sperm (82.7 +/- 7.2%). Additionally, the fertilizing capacity of post-thaw sperm was investigated with a standardized sperm to egg ratio 500:1. There is a linear regression relationship between the percentage of motile post-thaw sperm and fertilizing capability. These data demonstrate that 12-21% DMSO can provide good protection to the sperm during the freezing-thawing process. (c) 2006 Elsevier B.V. All rights reserved.

长白山火山成因—物理机制和化学演化

This thesis is one of the contributions to NSFC project, “The Changbaishan Volcanism and its Links to the Northeast Asia Tectonic System”. The thesis presents our most recent works on Changbaishan Volcanism, on two aspects as (1) the chemical evolution of the Cenozoic volcanism and the physical links of magma genesis, (2) the Holocene activity of the Tianchi Volcano and risks of potential eruption. 1. Chemical evolution and physical links to the Changbaishan Volcanism Physical links to the Chanbaishan Volcanism, just like origins of most of the volcanisms in eastern China, has long been an enigma. A large scale of volcanic activity has dominated many places of eastern China in Meso-Cenozoic. Activity of these volcanisms in eastern China covers several quite different blocks, covers variety of tectonics, and covers a period of time over 200 million years. Such a large-scale and long-lived volcanism in a continental area challenges our knowledge on dynamics of the Earth’s interior. Some works on “Diwa” hypothesis and “lithospheric thinning” hypothesis present possible links between volcanisms and dynamic evolutions of the earth’s interior, but still cannot interpret where are the sources of the heat and fluid, which are essential to the volcanisms. Based on the study of this thesis, we suggest that dynamics of the deep subduction of western Pacific Plate is the critical factor to the Changbaishan Volcanism and volcanisms in NE China, and maybe even essential to most of the Meso-Cenozoic volcanisms in eastern China. In NE China, stagnant slabs flatted in the mantle transition zone (MTZ, ca. 660 km deep) transport and release significant hydrous fluid to the upper mantle. Metamorphism of the deep-subducted slabs and hence a series of mineral phases play an important role in the water transport, exchange, restore, and release. Dehydrated fluid of the wet slab ascending from the MTZ fertile the upper mantle, and also provide upward heat flow which is essential to the magma genesis. Then magma and volcanism occur with the deep subduction from Mesozoic to mordern time in eastern China. To discribe the exact chemical characteristics of the deep subduction releated volcanics is very difficult, because few researches has contributed to the chemical behaviors of fluid and trace elments in the very deep interior of the Earth, such 660 km deep, 410km or 350km where the fluid may ascend and react. However we can still find some chemical characteristics of oceanic subduction. Basalts of the Changbaishan Volcanism have siginficant characteristics of potassium rich, and even can be called a potassic igneous province. If there are only two possible ways, recycled continentical crust or oceanic crust, to fertile the mantle potossium element as we know now, it’s easy to attribute this to the deep-subducted of the west Pacific Plate. To the eastern China, fluid inclusions in mantle xenoliths from the Cenozic basalts also reveal potassium-rich characteristics. This reveals that the same potassium feritle agents may occur in the mantle sources of eastern China. 2. Holocene activiy of the Tianchi Volcano As one of the large volcanic center and complex volcanic cone, the Tianchi Volcano is a dangerous active volcano, with several Holocene eruptions. Among these eruptions, the Millennium Eruption is regardede as one of the biggist eruptions in the world in the last 2000 years. To estimate the potential danger of volcanic eruption, we discuss two essential factors, as (i) volcanic history of Holocene eruptions, including volcanic geolgy, chronnology and chemistry, (ii) state, evolution and relationship of the magma chambers in mantle and crust beneath the Tianchi Volcano.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

水热条件下钾长石碱性分解反应机理的实验研究

It is well known that our country is short of water-soluble potassium, but rich in insoluble potassium ores. Based on the work of the formers, using the orthogonal and monofactor experiments, the author optimized the production technology of micro-porous potassium silicon calcium mineral fertilizer by non-stirring hydrothermal chemical reaction when the alkaline earth booster CaO was available. The influences of temperature、time、reactant ratio and water-solid ratio on the dissolution rate of production’s elements were studied by orthogonal experiments, and the production technology was further optimized by monofactor experiments. By XRD、SEM、EDS and dissolving experiments, it was systematically studied that the effects of the reactant ratio、reaction time and reaction temperature on the properties of the production obtained by the hydrothermal reaction between KAlSi3O8 and CaO. The results showed that：when changing of the reaction condition, the reaction productions included tobermorite、 hibschite、α-C2SH and K2Ca(CO3)2; among which, K2Ca(CO3)2 was not the first production containing potassium, but K2Ca(CO3)2 was synthesized by the reaction among KOH、Ca(OH)2 and CO2. Whether the phase was synthesized was related to not only the reaction condition, but also their physicochemical properties; when the reaction condition was changed, the changes of different phases were different. The results of XRD and dissolution rate experiments explained the dissolution characteristic of every element of hydrothermal productions very well, and the relation between the dissolution rate of element and the phase of productions poured a good illumination on the production technology. The results of SEM and EDS showed that: hydrogarnet looked like spherical, and its surface was covered by some productions including K phase and Ca、Si phase; but the morphology of tobermorite was platy or lamellar or needlelike, and parts of Si in the structure of tobermorite were substituted by Al，and some K+ cations were inserted into the Ca interlayer of tobermorite at the same time. It was the first time that the interface between KAlSi3O8 and Ca(OH)2 was observed directly by SEM and EDS after the hydrothermal reaction, and the mechanism of hydrothermal reaction of KAlSi3O8 and Ca(OH)2 was further discussed. These results indicated that: the Ca-KAlSi3O8 intermediate compound was formed at first, and some K was released into the solution and KOH was produced at the same time; the C-S-H phase appeared before hydrogarnet, and then hydrogarnet was synthesized when the chemical reaction was carried on; if the reaction was carried on furthermore, α-C2SH、tobermorite and other C-S-H phases of different atom ratio appeared. The author found that the structure of KAlSi3O8 would be more drastically destroyed if there were some reactants, such as Ca(OH)2 which reacted with KAlSi3O8 and new phases were formed after the hydrothermal reaction between KAlSi3O8 and alkaline solution of equal ionic strength was finished. With the combination of calcination and hydrothermal reaction methods, the dissolution rate of products were greatly improved when the hydrothermal reaction was carried out after KAlSi3O8 and CaCO3 were calcined. Furthermore, the author has tentatively explored how to evaluate the effects of the differences of the activity of lime on the dissolution properties of hydrothermal products.

东准噶尔和尔赛斑岩铜矿特征及其形成的构造背景

Hersai porphyry copper deposit(PCD) of eastern junggar, newly discovered copper deposit, is located at the eastern segment of the Xiemisitai-Kulankazigan-Zhifang-Qiongheba Paleozoic island arc, Eastern Junggar. The Hersai PCD is developed in a intrusive complex, characterized by intensive and multiform hydrothermal alteration, including potassic alteration, silification, chloritization，sericitization，kaolinitization and carbonatization. Granodiorite, grandiorite porphyry, granite and concealed explosion breccia are hosts of the ore bodies containing veinlet and disseminated ore. Ore-bearing granite (ZK107-1-9), granodiorite (ZK107-1-9) and Ore-barren granodiorite (HES2-1) are selected to date zircon U-Pb age by SHRIMP method, and have an age of 429.4±6.4Ma ,413.0±3.4Ma and 411.1±4.8Ma, respectively, showing that they were emplaced from Late Silurian to Early Devonian. In addition, sample ZK107-1-9 has some hydrothermal zircons with a weighted mean 206Pb/238U age of 404.9±3.7Ma which is interpreted to be related to the granodiorite porphyry. Re-Os dating of five molybdenite samples yielded a weighted average model age of 408.0±2.9Ma, indicating the metallogenic epoch of the Hersai PCD. The ore-forming age is close to the petrogenic time of garnodiorite (411-413Ma), this suggests the ore-forming porphyry is most possiblely granodiorite porphyry. Systematic major - trace elements and Rb-Sr-Sm-Nd-Pb-Hf isotopic characteristics were studied. Analysis results show that these intrusives have some interesting and special characteristics, as following:1) containing both calc-alkaline rocks and high potassium calc-alkaline rocks ; 2) have some characteristics of adakite, but not totally, such as much lower La/Yb ratios and no Eu anomaly or just faint Eu anomaly; 3) have an initial 87Sr/86Sr ratios(0.703852-0.704565) similar to that of BSE, positive εNd(t) values between 6.1 and 7.4, the initial 206Pb/204Pb values (17.576-17.912), 207Pb/204Pb values (15.400-15.453) , 208Pb/204Pb values (37.252-37.466) , and high εHf(t) values (10.2-15.4) close to the value of depleted mantle. These geochemical features suggest that these igneous rocks in the Hersai area not only have some characteristics of island arc, but also some characteristics that only appear in the continental margin arc. It is suggested that Hersai PCD is formed in the subduction setting by the partial melting of young crust. These works and advancements mentioned in the paper are helpful to understand the deposit geology, geochemistry and metallogenesis of Hersai PCD. It is also significant to understand mineralization and tectonic setting in the Qiongheba area.

青藏高原东缘新生代富钾碱性岩的年龄与岩石地球化学特征

The Cenozoic high-Potassium alkaline magma rocks are widely distributed in the eastern margin of Qinghai-Xizang (Tibet) plateau, such as Mangkang, Deqin, Jianchuan, Haidong in the western Yunnan Province, Yanyuan, Muli in the western Sichuan province, including syenite, minette and trachyte and lamprophyres, which formaed a large alkaline-rich magmatic rock zone along the Jinshajiang-Ailaoshan fault. Here we present detailed Geochemical and Geochronology study for the Cenozoic high-K alkline magma rocks from Mangkang, Deqin, Jianchuan, Haidong and Muli, Yanyuan, Yanbian, Yaoan (western Yangtze craton). Rocks of our target area include syenite, minette and trachyte. Geochronologic dating and compilation of existing age data suggest magmatism occurred at 32-38Ma and distribute along the Jinsha suture, from Jinping, Daping, Zhenyuan to Haidong, Jianchuan, Deqin, Mangkang, Zaduo to Qiangtang Bandaohu, Zhentouya. They all share same geochemical features such as rich in potassium and alkaline, rich in LREE, slightly negative Eu anomalies, negative anomalies in Nb, Ta, Ti,. These indicate they come from EMU mantle. Geochronologic dating on western Yangtze craton minette surgest minette in Haidong, Yanyuan, Yanbian, Yaoan, Deqin ocurred at 30-37Ma, well minette in Muli ocurred at IMa. Need more detailed geology study to find differece of these two episode magmatism.

西秦岭晚古生代弧前盆地沉积与成矿作用

The Western Qinling Orogenie belt in the Taibai-Fengxian and Xihe-Lixian areas can be subdivided into three units structurally from north to south, which are the island-arc, forearc basin and accretionary wedge, respectively. The forearc basin developed in the Late Paleozoic mainly controls sedimentation and some larger lead-zinc and gold deposits in the western Qinling. Stratigraphically, the island arc is dissected into the Liziyuan Group, the Danfeng Group and the Luohansi Group. The metavolcanic rocks include basic, intermediate and acidic rocks, and their geochemistry demonstrates that these igneous rocks generated in an island arc. Where, the basalts are subalkaline series charactered by low-medium potassium, with enriched LREE, negative Eu anomaly, and positive Nd anomaly. Cr-content of volcanic rocks is 2-3 times higher than that of island arc tholeiite all over the world. In addition, the lightly metamorphosed accretionary wedge in the areas of Huixian, Chengxian, Liuba and Shiqun is dominated by terrigenous sediments with carbonatite, chert, mafic and volcanic rocks. The age of the wedge is the Late Palaeozoic to the Trassic, while previous work suggested that it is the Silurian. The Upper Paleozoic between the island arc belt and accretionary wedge are mainly the sediments filled in the fore arc basin. The fillings in the forearc basin were subdivided into the Dacaiotan Group, the Tieshan Group, the Shujiaba Group and the Xihanshui Group, previously. They outcropped along the southern margins of the Liziyuan Group. The Dacaotan Group, the Upper Devonian, is close to the island arc complex, and composed of a suite of red and gray-green thick and coarse terrestrial elastics. The Shujiaba Group, the Mid-Upper Devonian, is located in the middle of the basin, is mainly fine-grained elastics with a few intercalations of limestone. The Xihanshui Group, which distributes in the southern of the basin, is mainly slates, phyllites and sandstones with carbonatite and reef blocks. The Tieshan Group, the Upper Devonian, just outcrops in the southwest of the basin, is carbonatite and clastic rocks, and deposited in the shallow -sea environment. The faults in the basin are mainly NW trend. The sedimentary characteristics, slump folds, biological assemblages in both sides of and within those faults demonstrate that they were syn-sedimentary faults with multi-period activities. They separated the forearc basin into several sub-basins, which imbricate in the background of a forearc basin with sedimentary characteristics of the piggyback basin. The deep hydrothermal fluid erupted along the syn-sedimentary faults, supported nutrition and energy for the reef, and resulted in hydrothermal-sedimentary rocks, reef and lead-zinc deposits along these faults. The sedimentary facies in the basin varies from the continental slope alluvial fan, to shallow-sea reef facies, and then to deep-water from north to south, which implies that there was a continental slope in the Devonian in the west Qinling. The strata overlap to north and to east respectively. Additionally, the coeval sedimentary facies in north and south are significantly different. The elastics become more and more coarser to north in the basin as well as upward coarsing. These features indicate prograding fillings followed by overlaps of the different fans underwater. The paleocurrent analyses show that the forearc basin is composed of thrust-ramp-basins and deep-water basins. The provenance of the fillings in the basin is the island arc in the north. The lead-zinc deposits were synchronous with the Xihanshui Group in the early stage of development of the forearc basin. They were strongly constrained by syn-sedimentary faults and then modified by the hydrothermal fluids. The gold deposits distributed in the north of the basin resulted from the tectonic activities and magmatism in the later stage of the basin evolution, and occurred at the top of the lead-zinc deposits spatially. The scales of lead-zinc deposits in the south of the basin are larger than that of the gold-deposits. The Pb-Zn deposits in the west of the basin are larger than those in the east, while the Gold deposits in the west of the basin are smaller than those in the east. Mineralizing ages of these deposits become younger and younger to west.

大兴安岭南段中生代火山-侵入杂岩带的双层叠置构造体制兼论滇中武定、易门碳酸质火山岩年代、来源及矿库与找矿研究

These are two parts included in this report. In the first part, the zonation of the complexes in its series, lithofacies, the depth of magma source and chambers is discussed in detailed for the first time based on the new data of petrol-chemistry, isotopes, tectono-magma activity of Mesozoic volcano-plutonic complexes in the southern Great Hinggan Mts. Then, the genetic model of the zonality, double overlapped layer system, is proposed. The main conclusions are presented as follows: The Mesozoic volcanic-plutonic complexes in the southern Great Hinggan were formed by four stages of magma activity on the base of the subduction system formed in late Paleozoic. The Mesozoic magmatic activity began in Meso-Jurassic Epoch, flourished in late Jurassic Epoch, and declined in early Cretaceous Epoch. The complexes consist dominantly of acidic rocks with substantial intermediate rocks and a few mefic ones include the series of calc alkaline, high potassium calc alkaline, shoshonite, and a few alkaline. Most of those rocks are characterized by high potassium. The volcano-plutonic complexes is characterized by zonality, and can be divided mainly into there zones. The west zone, located in northwestern side of gneiss zone in Great Xinggan mountains, are dominated of high potassium basalts and basaltic andesite. The middle zone lies on the southeast side of the Proterozoic gneiss zone, and its southeast margin is along Huangganliang, Wushijiazi, and Baitazi. It composed of dominatly calc-alkaline, high potassium calc-alkaline rocks, deep granite and extrusive rhyolite. The east zone, occurring along Kesheketong Qi-Balinyou Qi-Balinzuo Qi, is dominated of shoshonite. In generally, southeastward from the Proterozoic gneiss zone, the Mesozoic plutons show the zones-mica granitites zone, hornblende-mica granitite zone, mica-hornblende granitite zone; the volcanic rocks also display the zones of calc alkaline-high potassium calc alkaline and shoshonites. In the same space, the late Paleozoic plutons also display the same zonality, which zones are combined of binary granite, granodiorite, quartz diorite and diorite southeast wards from the gneiss. Meso-Jurassic Epoch granite plutons almost distribute in the middle zone on the whole. Whereas late Jurassic Epoch volcanic rocks distribute in the west and east zone. This distribution of the volcano-plutonic complexes reveals that the middle zone was uplifted more intensively then the other zones in Meso-Jurassic and late Jurassic Epoches. Whole rock Rb-Sr isochron ages of the high potassium calc-alkaline volcanic rocks in the west zone, the calc-alkaline and high potassium calc-alkaline granite the middle zone, shoshonite in the east zone are 136Ma, 175Ma and 154Ma, respectively. The alkaline rocks close to the shoshonite zone is 143Ma and 126Ma. The isochron ages are comparable well with the K-Ar ages of the rocks obtained previously by other researchers. The compositions of Sr ans Nd isotopes suggest that the source of Mesozoic volcanic-plutonic complexes in Great Hinggan Mts. is mostly Paleo-Asia oceanic volcanic-sedimentary rocks, which probably was mixed by antiquated gneiss. The tectonic setting for Mesozoic magmatism was subductive continental margin. But this it was not directly formed by present west Pacific subduction. It actully was the re-working of the Paleozoic subduction system( which was formed during the Paleo-Asia ocean shortening) controlled by west Pacific subduction. For this reason, Although Great Hinggan Mts. is far away from west Pacific subduction zone, its volcanic arc still occurred echoing to the volcanic activities of east China, it, but the variation trend of potassium content in volcano-plutonic complexes of Great Hinggan is just reverse to ones of west Pacific. The primitive magmas occurred in the southern Great Hinggan Mts. Include high-potassium calc-alkaline basalt, high potassium calc-alkaline rhyolite, high potassium rhyolite, non-Eu negative anomaly trachy-rhyolite et al. Therefore, all of primitive magmas are either mafic or acid, and most of intermediate rocks occurring in the area are the products of Mesozoic acid magma contaminated by the Paleozoic volcanic- sedimentary rocks. The depth of those primitive magma sources and chambers gradually increase from northwest to southeast. This suggests that Paleozoic subduction still controlled the Mesozoic magmatism. In summary, the lithosphere tectonic system of the southern Great Hinggan Mts. controlling Mesozoic magmatism is a double overlapped layer system developing from Paleozoic subduction system. For this reason, the depth of crust of the southern Great Hinggan Mts. is thicker than that of its two sides, and consequently it causes regional negative gravity abnormity. The second part of this report shows the prolongation of the research work carried on in my doctor's period. Author presents new data about Rb-Sr and Sm-Nd isotopic compositions and ages, geochamical features, genesis mineralogy and ore deposit geology of the volcanic rocks in Kunyang rift. On the base of the substantial work, author presents a prospect of copper bearing magnetite ore deposit. The most important conclusions are as follows: 1. It is proved that all of these carbonatites controlled by a ringing structure system in Wuding-Lufeng basin in the central Yunnan were formed in the Mesoproterozoic period. Two stages could be identified as follows: in the first stage, carbonatitic volcanic rocks, such as lavas(Sm-Nd, 1685Ma), basaltic porphyrite dykes(Sm-Nd, 1645Ma), pyroclastic rocks and volcaniclastic sedimentary rocks, formed in the outer ring; in the second stage, carbonatitic breccias and dykes(Rb-Sr, 1048 Ma) did in the middle ring. The metamorphic age of the carbonatitic lavas (Rb-Sr, 893 Ma) in the outer ring was determined. The magma of carbonatitic volcanic rocks derived mainly form enriched mantle whose basement is depleted mantle that had been metasomated by mantle fluid and contaminated by Archaean lower crust. Carbonatitic spheres were discovered in ore bearing layers in Lishi copper mining in Yimen recently, which formed in calcite carbonatitic magma extrusion. This discovery indicates that the formation of copper ore deposit genesis relates to carbonatitic volcanic activity. The iron and copper ore deposits occurring in carbonatitic volcanic- sedimentary rocks in Kunyang rift results from carbonatitic magmatism. Author calls this kind of ore deposits as subaqueous carbonatitic iron-copper deposit. The magnetic anomaly area in the north of Lishi copper mining in Yimen was a depression more lower than its circumference. Iron and copper ores occurrig on the margin of the magnetic anomaly are volcanic hydrothermal deposit. The magnetic body causing the magnetic anomaly must be magnetite ore. Because the anomaly area is wide, it can be sure that there is a large insidious ore deposit embedding there.

Determination of urinary nucleosides by direct injection and coupled-column high-performance liquid chromatography

A coupled-column liquid chromatographic method for the direct analysis of 14 urinary nucleosides is described. Efficient on-line clean-up and concentration of 14 nucleosides from urine samples were obtained by using a boronic acid-substituted silica column (40 turn x 4.0 mm I.D.) as the first column (Col-1) and a Hypersil ODS2 column (250 mm x 4.6 mm I.D.) as the second column (Col-2). The mobile phases applied consisted of 0.25 mol/L ammonium acetate (pH 8.5) on Col-1, and of 25 mmol/L potassium dihydrogen phosphate (pH 4.5) on Col-2, respectively. Determination of urinary nucleosides was performed on Col-2 column by using a linear gradient elution comprising 25 mmol/L potassium dihydrogen phosphate (pH 4.5) and methanol-water (60:40, v/v) with UV detection at 260 nm. Urinary nucleosides analysis can be carried out by this procedure in 50 min requiring only pH adjustment and the protein precipitation by centrifugation of urine samples. Calibration plots of 14 standard nucleosides showed excellent linearity (r > 0.995) and the limits of detection were at micromolar levels. Both of intra- and inter-day precisions of the method were better than 6.6% for direct determination of 14 nucleosides. The validated method was applied to quantify 14 nucleosides in 20 normal urines to establish reference ranges. (c) 2005 Elsevier B.V. All rights reserved.

Efeito do reflorestamento com diferentes espécies sobre os atributos químicos em solo de cerrado.

RESUMO: O objetivo desse trabalho foi avaliar o efeito do reflorestamento com eucalipto (Eucalyptus camaldulensis), carvoeiro (Sclerolobium paniculatum) , pinus (Pinus tecunumanii) e baru (Dipteryx alata) sobre os teores de nutrientes e de carbono orgânico do solo em comparação com uma área sob vegetação de Cerrado. Foram coletadas amostras de solo nas camadas 0 cm -5 cm, 5 cm - 10 cm, 10 cm - 20 cm, 20 cm - 30 cm, 30 cm - 40 cm e 40 cm - 60 cm, em um povoamento de baru plantado em 1987, um de carvoeiro plantado em 1985, um de pinus plantado em 1984, um de eucalipto plantado em 1983 e em uma área adjacente com vegetação nativa de Cerrado. Cada amostra foi composta por dez subamostras por parcela e por profundidade, coletadas entre as linhas. Os atributos químicos analisados foram: pH em água, alumínio trocável, H + Al (acidez potencial), fósforo e potássio disponíveis, cálcio e magnésio trocáveis e carbono orgânico. Os plantios de eucalipto e de carvoeiro aumentaram significativamente os teores de carbono orgânico do solo na camada de 0 cm a 5 cm. Os teores de fósforo foram muito baixos em todas as camadas avaliadas e não foram afetados pelo reflorestamento. O plantio de pinus acarretou queda significativa no teor de potássio, de cálcio e de magnésio até a camada de 30 cm a 40 cm. A partir de 20 cm de profundidade houve redução do pH do solo sob no plantio de pinus comparado com a área de Cerrado. ABSTRACT: The objective of this paper was to evaluate the effect of reforestation with eucalyptus (Eucalyptus camaldulensis), carvoeiro (Sclerolobium paniculatum) , pinus (Pinus tecunumanii) and baru (Dipteryx alata) on soil carbon and nutrients contents in comparison to virgin area of Cerrado. Samples of soil were collected down in 0 cm - 5 cm, 5 cm - 10 cm, 10 cm - 20 cm, 20 cm - 30 cm, 30 cm - 40 cm e 40 cm - 60 cm layers in a plantation of baru planted in 1987, one of carvoeiro planted in 1985, one of pinus planted in 1984, one of eucalyptus planted in 1983 and an adjacent area of Cerrado. Every sample was composed by ten sub-samples, by plot by depth, collected between the rows. Water pH, exchangeable aluminum, exchangeable H + Al (total acidity), suitable phosphorus, suitable potassium, exchangeable calcium, exchangeable magnesium and organic carbon contents were evaluated. Eucalyptus and carvoeiro planting increased significantly soil organic carbon contents in 5 cm - 10 cm layer. The levels of phosphorus were very low in all evaluated layers and were not affected by reforestation. Pinus planting decreased significantly potassium, calcium and magnesium contents until 30 cm - 40 cm layer. There was pH reduction after 20 cm of depth in pinus planting compared with cerrado area.

Formation of channels for fast-ion diffusion in alkali silicate melts: A quasielastic neutron scattering study

Kargl, Florian; Meyer, A.; Koza, M.M.; Schober, H., (2006) 'Formation of channels for fast-ion diffusion in alkali silicate melts: A quasielastic neutron scattering study', Physical Review B: Condensed Matter and Materials Physics 74 pp.14304 RAE2008