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.

中国北方中新世风尘物质来源及古气候的地球化学指示

The most prominent tectonic and environmental events during the Cenozoic in Asia are the uplift of the Himalaya-Tibetan plateau, aridification in the Asian interior, and onset of the Asian monsoons. These caused more humid conditions in southeastern China and the formation of inland deserts in northwestern China. The 22 Ma eolian deposits in northern China provide an excellent terrestrial record relative to the above environmental events. Up to date, many studies have focused on the geochemical characters of the late Mio-Pleistocene eolian deposits, however, the geochemical characteristics of the Miocene loess and soils is still much less known. In this study, the elemental and Sr-Nd isotopic compositions of the eolian deposits from the Qinan (from 22.0 to 6.2 Ma) and the Xifeng (from 3.5 Ma until now) loess-soil sections were analyzed to examine the grain size effects on the element concentrations and the implications about the dust origin and climate. The main results are as follows: 1. The contents of Si, Na, Zr and Sr are higher in the coarser fractions while Ti and Nb have the highest contents in the 2-8 μm fractions. Al, Fe, Mg, K, Mn, Rb, Cu, Ga, Zn, V, Cr, Ni, LOI have clear relationships with grain-size, more abundant in the fine fraction while non significant relationship is observed for Y. Based on these features, we suggest that K2O/Al2O3 ratio can be used to address the dust provenance, and that VR (Vogt ratio = (Al2O3+K2O)/(MgO+CaO+Na2O)) can be used as a chemical weathering proxy for the Miocene eolian deposits because of their relative independence on the grain size. Meanwhile, SiO2/Al2O3 molar ratio is a best geochemical indicator of original eolian grain size, as suggested in earlier studies. 2. Analyses on the Sr and Nd isotope composition of the last glacial loess samples (L1) and comparison with the data from the deserts in northern China suggest that that Taklimakan desert is unlikely to be the main source region of the eolian dust. In contrast, these data suggest greater contributions of the Tengger, Badain Jaran and Qaidam deserts to the eolian dust during the last glacial cycle. Since the geochemical compositions (major, trace, REE and Sr, Nd isotope) of loess samples for the past 22 Ma are broadly similar with the samples from L1, these data trend to suggest relatively stable and insignificant changes of dust sources over the past 22 Ma. 3. Chemical weathering is stronger for Miocene paleosol samples than for the Plio-Pleistocene ones, showing warmer/more humid climatic conditions with a stronger summer monsoon in the Miocene. However, chemical weathering is typical of Ca-Na removal stage, suggesting a climate range from semiarid to subhumid conditions. These support the notion about the formation of a semi-arid to semi-humid monsoonal regime by the early Miocene, as is consistent with earlier studies.

东喜马拉雅构造结新生代碰撞变形与岩石圈演化

The Eastern Himalayan Syntaxis (EHS) is one of the strongest deformation area along the Himalayan belt resulted from the collision between Indian plate and the Eurasian Plate since the 50～60Ma, and has sensitivity tracked and preserved the whole collisional processes. It should depend on the detail geological investigations to establish the deformational accommodate mode, and the uplift history, to elucidate the deep structure and the crust-mantle interaction of the Tibet Plateau of the EHS. The deep-seated (Main Mantle Thrusts) structures were exhumed in the EHS. The MMT juxtapose the Gangdese metamorphic basement and some relic of Gangdese mantle on the high Himalayan crystalline series. The Namjagbawa group which is 1200～1500Ma dated by U/Pb age of zircon and the Namla group which is 550Ma dated by U/Pb age of zircon is belong to High Himalayan crystalline series and Gangdese basement respectively. There is some ophiolitic relic along the MMT, such as metamorphic ocean mantle peridotite and metamorphic tholeiite of the upper part of ocean-crust. The metamorphic ocean mantle peridotites (spinel-orthopyroxene peridotite) show U type REE patterns. The ~(87)Sr/~(86)Sr ratios were, 0.709314～0.720788, and the ~(143)Nd/~(144)Nd ratios were 0.512073～0.512395, plotting in the forth quadrant on the ~(87)Sr/~(86)Sr-~(143)Nd/~(144)Nd isotope diagram. Some metamorphic basalt (garnet amphibolite) enclosures have been found in the HP garnet-kynite granulite. The garnet amphibolites can be divided two groups, the first group is deplete of LREE, and the second group is flat or rich LREE, and their ~(87)Sr/~(86)Sr, ~(143)Nd/~(144)Nd ratios were 0.70563～0.705381 and 0.512468～0.51263 respectively. Trace element and isotopic characteristics of the garnet amphibolites display that they formed in the E-MORB environment. Some phlogolite amphibole harzburgites, which exhibit extensive replacement by Phl, Amp, Tc and Dol etc, were exhumed along the MMT. The Phl-Amp harzburgites are rich in LREE and LILE, such as Rb, K etc, and depletes Eu (Eu~* = 0.36 ～ 0.68) and HFSE, such as Nb, Ta, Zr, Hf, P, Ti etc. The trace element indicate that the Phl-Amp harzburgites have island arc signature. Their ~(87)Sr/~(86)Sr are varied from 0.708912 to 0.879839, ~(143)Nd/~(144)Nd from 0.511993 to 0.512164, ε Nd from- 9.2 to - 12.6. Rb/Sr isochrone age of the phlogolite amphibole harzburgite shows the metasomatism took place at 41Ma, and the Amp ~(40)Ar/~(39)Ar cooling age indcate the Phl-Amp harzburgite raising at 16Ma. There is an intense crust shortening resulted from the thrust faults and folds in the Cayu block which is shortened more 120km than that of the Lasha block in 35～90Ma. With the NE corner of the India plate squash into the Gangdese arc, the sinistral Pai shear fault and the dextral Aniqiao shear fault on the both sides of the Great bent of Yalun Zangbu river come into active in 21～26Ma. On the other hand, the right-lateral Gongrigabu strike-slip faults come into activity at the same period, a lower age bound for the Gongrigabu strike-slip fault is estimated to be 23～24Ma from zircon of ion-probe U/Pb thermochronology. The Gongrigabu strike-slip faults connect with the Lhari strike-slip fault in the northwestern direction and with the Saganing strike-slip at the southeastern direction. Another important structure in the EHS is the Gangdese detachment fault system (GDS) which occurs between the sedimental cover and the metamorphic basement. The lower age of the GDS is to be 16Ma from the preliminary 40Ar/39Ar thermochronology of white mica. The GDS is thought to be related to the reverse of the subducted Indian crust and the fast uplift of the EHS. Structural and thermochronology investigation of the EHS suggest that the eastern Tibet and the western Yunnan rotated clockwise around the EHS in the period of 35～60Ma. Later, the large-scale strike-slip faults (RRD, Gaoligong and Saganing fault) prolongate into the EHS, and connect with the Guyu fault and Gongrigabu fault, which suggest that the Indianchia block escape along these faults. Two kind of magmatic rocks in the EHS have been investigated, one is the mantle-derived amphibole gabbro, dioposide diorite and amphibole diorite, another is crust origin biotit-garnet adamellite, biotit-garnet granodiorite and garnet-amphibole-biotite granite. The amphibole gabbro dioposite diorite and amphibole diorite are rich in LREE, and LILE, such as Ba, Rb, Th, K, Sr etc, depleted in HFSE, such as Nb, Ta, Zr, Hf, Ti etc. The ratio of ~(87)Sr/~(86)Sr are from 0.7044 to 0.7048, ~(143)Nd/~(144)Nd are from 0.5126 to 0.5127. The age of the mantle origin magamatic rocks, which result from the partial melt of the raising and decompression anthenosphere, is 8Ma by ~(40)Ar/~(39)Ar dating of amphibole from the diorite. The later crust origin biotite-garnet adamellite, biotite-garnet granodiorite and garnet-amphibole-biotite granite are characterized by aboudance in LREE, and strong depletion of Eu. The ratios of ~(87)Sr-~(86)Sr are from 0.795035 to 0.812028, ~(143)Nd/~(144)Nd from 0.51187 to 0.511901. The ~(40)Ar/~(39)Ar plateau age of the amphibole from the garnet-amphibole-biotite granite is 17.5±0.3Ma, and the isochrone age is 16.8±0.6Ma. Their geochemical characteristics show that the crust-derived magmatic rocks formed from partial melting of the lower curst in the post-collisional environment. A group of high-pressure kaynite-garnet granulites and enclave of high-pressure garnet-clinopyroxene grnulites and calc-silicate grnulites are outcroped along the MMT. The peak metamorphic condition of the high-pressure granulites yields T=800～960 ℃, P=1.4～1.8Gpa, corresponding the condition of 60km depth. The retrograde assemblages of the high-pressure grnulites occur at the condition of T=772.3～803.3 ℃, P=0.63～0.64Gpa. The age of the peak metamorphic assemblages are 45 ～ 69Ma indicated by the zircon U/Pb ion-plobe thermochronology, and the retrograde assemblage ages are 13～26Ma by U/Pb, ~(40)Ar/~(39)Ar thermochronology. The ITD paths of the high-pressure granulites show that they were generated during the tectonic thickening and more rapid tectonic exhumation caused by the subducting of the Indian plate and subsequent break-off of the subducted slab. A great deal of apatite, zircon and sphene fission-track ages, isotopic thermochronology of the rocks in the EHS show that its rapid raising processes of the EHS can be divided into three main periods. There are 35～60Ma, 13～25Ma, 0～3Ma. 3Ma is a turn in the course of raising in the EHS which is characterized by abruptly acceleration of uplifting. The uplift ratios are lower than 1mm .a~(-1) before 3Ma, and higher than 1mm .a~(-1) with a maximum ratio of 30mm .a~(-1) since 3Ma. The bottom (knick point) of the partial anneal belt is 3.8km above sea level in the EHS, and correspond to age of 3Ma determined by fission-track age of apatite. The average uplift ratio is about 1.4 mm .a~(-1) below the knick point. The EHS has raised 4.3km from the surface of 2.36km above sea level since 3Ma estimated by the fossil partial anneal belt of the EHS. We propose a two-stage subduction model (B+A model) basing on Structural, thermochronological, magmatical, metamorphic and geophysical investigations of the EHS. The first stage is the subduction of the Indian continental margin following after the subduction of the Tethys Ocean crust and subsequent collision with the Gangdese arc, and the second stage is the Indian crust injecting into the lower crust and upper mantle of the Tibet plateau. Slab break-off seems to be occurred between these two stages.

藏东及滇东南新生代钾质岩浆作用及其深部制约

The dissertation focuses on the petrology, geochemistry of the volcanic rocks in east Tibet and southeast Yunnan. It lucubrates the Magmatic process, forming mechanism and the possible tectonic settings of the volcanic rocks. The volcanic rocks of Nangqen basin in east Tibet, Qinghai province are mainly Cenozoic intermediate-acid shoshonites. The rocks are LREE enriched and the LREE/HREE = 3～34; (La/Yb)_N = 18.17-53.59, and ΣREE 222～1260μg/g. There are no Eu anomaly, and Nb, Ta, Zr, Hf, Ti are markedly depleted. The isotopic composition is ~(87)Sr/~(86)Sr = 0.70497～0.70614, ~(206)Pb/~(204)Pb = 18.622～18.974, ~(208)Pb/~(204)Pb = 38.431～38.996, ~(207)Pb/~(204)Pb = 15.511～15.613, respectively. K-Ar age of the whole rocks and the single mineral are between 32.0-36.5Ma. Based on the trace elements and isotopic elements, we get the conclusion that the partial melting is one of the dominated forming mechanisms for the volcanic rocks in Naneqen basin. The magma did not experience the crustal contamination en route to the surface; however, the complex mixture took place in the upper mantle before the melt was formed. There are at least two kinds of mixed sources that can be identified. The basalt in southeast Yunnan province is studied. They are distributed in Maguan, Tongguan, and Pingbian County, which is located on the both sides of the Red River belt, and the ultrabasic xenolith are cursory introduced. The volcanic rocks belongs to the alkali series, which can be subdivided into trachybasalt and basanite(Ol normal molecule >5). The volcanic rocks are characteristics by high Ti and low Mg#. According to the magma calculation model, the original rocks of the basalt in southeast Yunnan province are Spinel Lherzolite in Tongguan, Garnet Lherzolite in Pingbian and Maguan, while Togguan undergoes 2-5 percent and percent of partial melting, whereas volcanism in Maguan and Pingbian was so complex to calculate. The fractional crystallization took place during the magma evoltion in southeast Yunnan. The basalt is enriched in LREE with LREE/HREE=9.23-20.19. All of the trace elements display weak Nb, Ta peak, and the depletion of Zr, Hf and Ti in Maguan and pingbian represent the presence of Garnet in the source. The composition of the isotope ratio are ~(87)Sr/~(86)Sr = 0.70333-0.70427, ~(143)Nd/~(144)Nd = 0.512769-0.512940, ~(206)Pb/~(204)Pb = 18.104-18.424, ~(207)Pb/~(204)Pb = 15.483 -15.527; ~(208)Pb/~(204)Pb = 37.938-38.560, respectively, which shows the characteristics of the HIMU type OIB. The volcanic rocks of the southwest Yunnan are derived from the enriched, OIB type mantle sources by synthesizing all the data from trace and isotope elements. It is similar to that of the volcanic rocks in Hawaii, a typical kind of the mixtures of the recycled oceanic crust plume and depleted asthenosphere. To sum up, the volcanic rocks in southeast Yunnan are formed by the intraplate hotpot volcanism.

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

河北寿王坟铜矿成矿定年及同位素地球化学特征

Samples from carbonate wall-rocks, skarn, ore of skarn type, later calcite vein, and ore of porphyry type in Shouwangfen copper deposit district were collected. Systematic study was carried out on carbon, oxygen, rubidium, strontium and sulfur isotope compositions of carbonates and sulfides in these samples. The first Isochron dating by the Rb-Sr isotopes in chalcopyrite of ore sub-sample was done as well. The following conclusions were obtained. The age (113.6±4.3Ma), obtained by Rb-Sr isotope isochron dating of chalcopyrite and pyrite from sub-sample of skarn ores, probably represents the true mineralization age of skarn ores. That demonstrates the genetic relationship between granodiorite in Shouwangfen complex and skarn copper ores. On the other hand, the Rb-Sr isochron age (73±15Ma) of chalcopyrite from porphyry ores is a little incredible because of bad synthesizing evaluation. But combined with other age data of igneous rocks, it implies the possibility of hydrothermal mineralization in connection with magma activity during the fourth period of Yanshanian in Hebei Province, even in the whole northern edge of Huabei continental block. Together from structure analysis of sulfide sub-samples, from pretreating preccedure of Rb-Sr isotope isochron and its' valuating, we found out that Rb-Sr isotope isochron of sulfide sub-samples is influenced by the crystal structure of sulfides. That is, sulfide ores with very big crystals are not suitable for sub-sample isochron. Carbon, oxygen, sulfur and strontium compositions, of different minerals in these two kinds of ores, imply that the ore-forming hydrothermal fluids were probably derived from magma deep under the crust. The calcite ~(87)Sr/~(86)Sr ratios from the porphyry are consistent to the initial 87Sr/86Sr ratio of the Rb-Sr isochron of chalcopyrite and pyrite in the skarn ore, indicating that these two kinds of ores have the same source characteristic, although the porphyry deposit was formed probably 40 million years later than the skarn one according to our dating results. Skarn and skarn ores are usually considered as interaction product between carbonate wall-rocks and magmatic fluids, but the carbon of the sedimentary carbonate seems not involved in the skarn ores. Considering the connection of magmatic processes and hydrothermal ore formation in the Shouwangfen district, particularly, the spatial distribution of skarn-type and porphyry-type ores, it is possible that the Shouwangfen ore district corresponds to a hydrothermal ore-forming system, which was promoted by high-intruding magmatic rocks. Systematic stable isotopic research can help to reveal the upper part of this hydrothermal ore-forming system, which mainly related to heated and circulating meteoric water, and the lower part principally related to ascending magmatic fluids. Both skarn and porphyry ore-bodies are formed by up-intruding magmatic fluids (even more deep mantle-derived fluids).

7.0Ma以来中国黄土粉尘源区的化学风化历史研究-Sr同位素比值的证据

To investigate the changes in the chemical weathering intensity of dust source region in Asia continent, ~(87)Sr/~(86)Sr ratios of acid-washed residues from the loess deposits in China and Tajikistan were analyzed, respectively. The results and conclusions are listed as below. 1. The oscillation of ~(87)Sr/~(86)Sr ratios of acid-insoluble residues in the Chinese Loess Plateau was mainly attributed to the chemical weathering intensity of the source region and the grain size. Counteracted the effect of particle size, the calibrated 87Sr/S6Sr ratio can be used as a proxy for the chemical weathering intensity of the source region. 2. The Sr/ Sr ratios of red clay-loess sequence from the Loess Plateau indicate that the chemical weathering intensity of the dust source region between 7.0 and 2.6 Ma is stronger than that in the Quaternary period. This also suggests a general decline in chemical weathering intensity of the source region from 2.6 Ma to the present. Such pattern is more remarkable since 1.0 Ma BP. 3. The ~(87)Sr/~(86)Sr ratios of the Tajik loess during 0.8-1.8 Ma is much more higher than those from 0.8 Ma to the present. This implies that the chemical weathering intensity of the source region in Central Asia is much stronger during 0.8-1.8 Ma than the period since 0.8 Ma. 4. The record of Sr isotope ratios from both sections shows an accelerating course of aridity of the Asian dust source region over the Quaternary period.

安多地区早中侏罗世岩浆岩岩石地球化学和同位素年代学研究及其对构造演化的制约

Anduo area is located in the Central Tibet, the middle segment of the Bangonghu-Nujiang suture. Anduo Block is the northern part of Lhasa terrane. The relationships among the different geological bodies were determined during the 1: 250000 regional geological surveying. Petrography, petrologic geochemistry, isotopic geochemistry and geochronology of igneous rocks from the suture and granitoids from Anduo Block were analyzed systematically as a whole for the first time. Then, their tectonic setting and history are discussed.Anduo ophiolitic melange consists of metamorphic peridotites, cumulates, plagiogranites, sheeted dykes swarm, pillow lava and radiolarian cherts. The concentration of Cr and Ni in the metamorphic peridotites is very high, with Mg# about 0.94 ~ 0.97, higher 87Sr/86Sr and Pb isotopic ratios, and lower 143Nd/i44Nd ratio. LREE is enriched relative to HREE and positive Eu anomaly is very clear. The REE distribution curve is U shape. Nb and Ta anomalies from cumulate gabbro and sheeted dyke swarm are not clear, while that are slightly negative from pillow lava. Plagiogranite belongs to strong calc-alkaline series with high Si, middle Al, low Fe, Mg and low K contents. Eu anomaly (~ 1.23) from plagiogranites is slightly positive. The character of all components of ophiolite is similar to that of the MORB, while to some extent the ophiolite was influenced by crustal material. Anduo ophiolite formed in a mature back-arc basin. Additionally, intermediate acidity volcanic rocks within Anduo phiolite melange are island arc calc-alkline rocks related to ocean subduction.The early-middle Jurassic plutonic rocks are tonalite, granodiorite bearing-phenocryst, magaporphyritic hornblende monzogranite, magaporphyritic monzogranite, monzogranite bearing-phenocryst and syenogranite in turn. They belong to calc-alkaline series which developed from middle K to high K series temporally. REE distribution curves of all plutonic rocks are similar and parallel to each other. SREE and negative Eu anomaly values decrease. In the multi-element spider diagram, the curves of different plutons are similar to each other, but troughs of Nb, Sr, P and Ti from young plutons become more evident. This suggests that thereare some closely petrogenetic affinities among plutonic rocks which make up amagma plutonism cycle of the early-middle Jurassic. Magma source is mainly crustal,but abundant mafic microgranular enclaves within granitoids indicate that crastalmagma should be mixed with mantle-derived magma and the mantle-derived magmadecreased subsequently. Tonalite has features of I-type granite, magaporphyriticmonzogranite is transition type, and monzogranite bearing-phenocryst is S-typegranite. The characteristic of granitoids from Anduo Block suggest that the formingtectonic setting is active continental margin.Reliable zircon U-Pb SHRIMP ages are obtained in the study area firstly. Plagiogranite from the Anduo ophiolite of the Bangonghu-Nujiang suture is 175.1 Ma, and granitoids from Anduo Block is 172.6-185.4 Ma. Additionally, plagioclase from the plagiogranite dates a 40Ar/39Ar age of 144 Ma, while biotite and hornblend from granitoids of Anduo Block give a 163-165 Ma.Similar cooling ages of plagiogranite from the Anduo ophiolitic melange and granitoids from Anduo Block and the spatial distribution of the ophiolitic rocks between Anduo, Naqu, and Shainzha area suggest that bilateral subduction of the Bangonghu-Nujiang oceanic basin took place in the early-middle Jurassic. During this subduction, Anduo ophiolitic rocks were related to north subduction of the Bangonghu-Nujiang oceanic basin and Anduo back-arc basin spreading, while granitoids from Anduo Block were related to south subduction.

Impact of gene variants on sex-specific regulation of human Scavenger receptor class B type 1 (SR-BI) expression in liver and association with lipid levels in a population-based study.

BACKGROUND: Several studies have noted that genetic variants of SCARB1, a lipoprotein receptor involved in reverse cholesterol transport, are associated with serum lipid levels in a sex-dependent fashion. However, the mechanism underlying this gene by sex interaction has not been explored. METHODS: We utilized both epidemiological and molecular methods to study how estrogen and gene variants interact to influence SCARB1 expression and lipid levels. Interaction between 35 SCARB1 haplotype-tagged polymorphisms and endogenous estradiol levels was assessed in 498 postmenopausal Caucasian women from the population-based Rancho Bernardo Study. We further examined associated variants with overall and SCARB1 splice variant (SR-BI and SR-BII) expression in 91 human liver tissues using quantitative real-time PCR. RESULTS: Several variants on a haplotype block spanning intron 11 to intron 12 of SCARB1 showed significant gene by estradiol interaction affecting serum lipid levels, the strongest for rs838895 with HDL-cholesterol (p=9.2x10(-4)) and triglycerides (p=1.3x10(-3)) and the triglyceride:HDL cholesterol ratio (p=2.7x10(-4)). These same variants were associated with expression of the SR-BI isoform in a sex-specific fashion, with the strongest association found among liver tissue from 52 young women<45 years old (p=0.002). CONCLUSIONS: Estrogen and SCARB1 genotype may act synergistically to regulate expression of SCARB1 isoforms and impact serum levels of HDL cholesterol and triglycerides. This work highlights the importance of considering sex-dependent effects of gene variants on serum lipid levels.

Isotopic imprints of mountaintop mining contaminants.

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ(34)SSO4), carbon isotopes in dissolved inorganic carbon (δ(13)CDIC), and strontium isotopes ((87)Sr/(86)Sr). The data show that δ(34)SSO4, δ(13)CDIC, Sr/Ca, and (87)Sr/(86)Sr measured in saline- and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low (87)Sr/(86)Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high (87)Sr/(86)Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct (87)Sr/(86)Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive (87)Sr/(86)Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.

Boron and strontium isotopic characterization of coal combustion residuals: validation of new environmental tracers.

In the U.S., coal fired power plants produce over 136 million tons of coal combustion residuals (CCRs) annually. CCRs are enriched in toxic elements, and their leachates can have significant impacts on water quality. Here we report the boron and strontium isotopic ratios of leaching experiments on CCRs from a variety of coal sources (Appalachian, Illinois, and Powder River Basins). CCR leachates had a mostly negative δ(11)B, ranging from -17.6 to +6.3‰, and (87)Sr/(86)Sr ranging from 0.70975 to 0.71251. Additionally, we utilized these isotopic ratios for tracing CCR contaminants in different environments: (1) the 2008 Tennessee Valley Authority (TVA) coal ash spill affected waters; (2) CCR effluents from power plants in Tennessee and North Carolina; (3) lakes and rivers affected by CCR effluents in North Carolina; and (4) porewater extracted from sediments in lakes affected by CCRs. The boron isotopes measured in these environments had a distinctive negative δ(11)B signature relative to background waters. In contrast (87)Sr/(86)Sr ratios in CCRs were not always exclusively different from background, limiting their use as a CCR tracer. This investigation demonstrates the validity of the combined geochemical and isotopic approach as a unique and practical identification method for delineating and evaluating the environmental impact of CCRs.

Geochemical and isotopic evidence for seawater contamination of the hydrothermal system of Taal volcano, Luzon, the Philippines

The hydrologic structure of Taal Volcano has favored development of an extensive hydrothermal system whose prominent feature is the acidic Main Crater Lake (pH<3) lying in the center of an active vent complex, which is surrounded by a slightly alkaline caldera lake (Lake Taal). This peculiar situation makes Taal prone to frequent, and sometimes catastrophic, hydrovolcanic eruptions. Fumaroles, hot springs, and lake waters were sampled in 1991, 1992, and 1995 in order to develop a geochemical model for the hydrothermal system. The low-temperature fumarole compositions indicate strong interaction of magmatic vapors with the hydrothermal system under relatively oxidizing conditions. The thermal waters consist of highly, moderately, and weakly mineralized solutions, but none of them corresponds to either water-rock equilibrium or rock dissolution. The concentrated discharges have high Na contents (>3500 mg/kg) and low SO4/Cl ratios (<0.3). The Br/Cl ratio of most samples suggests incorporation of seawater into the hydrothermal system. Water and dissolved sulfate isotopic compositions reveal that the Main Crater Lake and spring discharges are derived from a deep parent fluid (T≃300°C), which is a mixture of seawater, volcanic water, and Lake Taal water. The volcanic end member is probably produced in the magmatic-hydrothermal environment during absorption of high-temperature gases into groundwater. Boiling and mixing of the parent water give rise to the range of chemical and isotopic characteristics observed in the thermal discharges. Incursion of seawater from the coastal region to the central part of the volcano is supported by the low water levels of the lakes and by the fact that Lake Taal was directly connected to the China sea until the sixteenth century. The depth to the seawater-meteoric water interface is calculated to be 80 and 160 m for the Main Crater Lake and Lake Taal, respectively. Additional data are required to infer the hydrologic structure of Taal. Geochemical surveillance of the Main Crater Lake using the SO4/Cl, Na/K, or Mg/Cl ratio cannot be applied straightforwardly due to the presence of seawater in the hydrothermal system.

A comparison of nitogen fate and transport in catchments underlain by high and low permeability aquifers using chemical and isotopic tools.

Variability in nitrogen fate and transport in different catchments types is often not considered. This research considers the importance of such nitrogen processes within groundwater pathways in two agricultural catchments in Ireland; a well drained catchment, underlain by karstified Carboniferous limestone, and a poorly drained catchment, underlain by Silurian greywacke.
Depth specific low-flow groundwater sampling was used to evaluate the hydrochemical stratification in groundwater. Groundwater samples, as well as surface water samples, along river courses were analysed for nitrogen species (NO3, NH4 and NO2) and nitrate isotopes (d15N and d18O) as well as field parameters and major ions
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The dominant nitrate (NO3) groundwater pathway in the poorly drained greywacke catchment is through the shallow weathered bedrock, as indicated by transmissivity values and the ionic and isotopic signatures, and a clear reduction in NO3 concentration is observed with depth. A similar chloride trend would suggest dilution is a major factor, however d15N and d18O isotopic values producing an enrichment ratio of 1.8 indicate that denitrification is also an important process involved in the fate of the NO3 within the groundwater flow system. This consistent trend with depth is in contrast to the stratification pattern observed in the karstified catchment. NO3 was not detected in the shallow groundwater pathway; the dominant groundwater pathway is in the deeper groundwater where there is little change in the nitrate isotope values with depth (d15N values range between 4.1 and 4.6 ‰). This deeper groundwater contributes the dominant proportion of the river flow through a number of springs. As a result, the deeper groundwater, springs and river have a similar ionic signature and NO3 concentration range (23 ± 3 mg/l). Despite this pattern, the NO3 isotopes show a distinct difference in isotopic values between the deeper groundwater in the diffuse karst and the springs indicating some denitrification is occurring during groundwater discharge into the river. Furthermore the isotopes give an indication of the variability of the spatial extent of the springs and the complexities of the fissures through which they are fed. The results of this study clearly show the importance of the geology in the fate and transport of NO3 in agricultural catchments.