First-principles Study on Equilibrium Sn Isotope Fractionations in Hydrothermal Fluids

Tin (Sn) isotope geochemistry has great potential in tracing geological processes. However, lack of equilibrium Sn isotope fractionation factors of various Sn species limits the development of Sn isotope geochemistry. Equilibrium Sn isotope fractionation factors (124Sn/116Sn and 122Sn/116Sn) among various Sn(II, IV) complexes in aqueous solution were calculated using first-principles calculations. The results show that the oxidation states and the change of Sn(II, IV) species in hydrothermal fluids are the main factors leading to tin isotope fractionation in hydrothermal systems. For the Sn(IV) complexes, Sn isotope fractionation factors depend on the number of H2O molecules. For the Sn(II) complexes, the Sn isotope fractionation between Sn(II)?F, Sn(II)?Cl and Sn(II)?OH complexes is mainly affected by the bond length and the coordination number of anion, whereas the difference in 1000lnβ values of Sn(II)?SO4 and Sn(II)?CO3 complexes is insignificant with the change of anion coordination number. By comparing the 1000lnβ values of all Sn(II, IV) complexes, the enrichment trend in heavy Sn isotopes is Sn(IV) complexes > Sn(II) complexes. The equilibrium Sn isotopic fractionation factors enhance our understanding of the tin transportation and enrichment processes in hydrothermal systems.     

北大别灰色片麻岩的岩石化学特征及大地构造背景

The principle component of the north Dabie metamorphic complex (NDC) is a suite of gray gneisses, which is compositionally comparable to the tonalite-trondjemite-granodiorite association. Gray gneisses, including amphibolite gneiss, amphibolite-plagioclase gneiss, quartzo-feldspar gneiss, have the SiO₂ contents ranging from 50％ to 75％ or more. On the SiO₂ variation diagram most of major oxide display a smooth trend from tonalitic gneiss to trondhjemitic or granitic rocks, implying a magmatic differentiation model for the origin of the gray gneisses. The differentiation was probably controlled by hornblende and plagioclase fractionation. The gray gneisses have lower ΣREE content with low grade fractionation of light REE/ heavy REE. On primary mantle-normalized REE fractional diagrams, the subparallel patterns indicate a cogenetic relation for all samples. All rocks are enriched in large ion lithophile (LIL) elements and depleted in high field strength (HFS) elements, as well as Nb at the level of primary mantle. The increasing of Nb depletion, the decreasing of Sr enrichment, and the transitional metal element Ti becoming greatly depleted with the increase of the SiO₂ in the rocks imply the fraction of mafic minerals and plagioclase. The granitoids have lower FeO, MgO, CaO contents, low FeO^*/ (FeO^*+MgO) ratios, and Nb and Y depletion. On Hf/3-Th-Ta (Nb) diagram, all plots set near the Hf-Th join and cumulate to Th corner, providing a calc-alkaline series of arc setting. All of these imply that the gray gneiss is of the calc-alkaline association formed in a volcanic arc.     

Oxygen Isotope Fractionation in TiO2 Polymorphs and Application to Geothermometry of Eclogites

Oxygen isotope fractionation in TiO2 polymorphs has been calculated by the modi-fied increment method .The results that rutile is enriched in ^18O relative to brookite but depleted in ^18O relative to anatase.Due to the same crystal structure ,oxygen isotope partitioning in the TiO2 polymorphs is determined by the cation-oxygen inter-atomic distances.The theoretical calibrations involving rutile are in fair agreement with known experimental measurements and empirical estimates.Application of the theoretic-cal quartz-rutile calibration to geothermometry of natural eclogite assemblages indicates the preservation of isotopic equilibrium at high temperatures.The isotopic temperatures calculated are only slightly lower than the non-isotopic temperatures,indicating the slow rates of exchange for oxygen diffusion in rutile.The kinetics of exchange for oxygen diffu-sion in rutile is accordingly estimated by reconciling the differences between the isotopic and the non-isotopic temperatures.The rates of exchange for oxygen diffusion in rutile should be smaller than those for hornblende,but may be equal to or greater than those for diopside.     

Oxygen Isotope Studies of Epithermal Systems：A Review

Numerous stable isotope studies of whole rocks and mineral separates in epithermal systems indi-cate that even though meteoric waters are dominant components in epithermal systems ,fluids of other origins,such as sedimentary or meta-sedimentary fluids,magmatic waters and even evolved meteoric waters ,may also play a role in the formation of epithermal ore deposits.Usually the more depleted the wall rocks,the larger the size of ore deposits ,and the least depletion degrees in whole rocks for economic mineralization are by about 3.5‰.The depletion in δ^18O in wall rocks,however,may be complicated by the superimposition of low temperature-hydration over high-temperature altera-tion or vice versa,the existence of primary low-^18O and high-^18O magmas ,and alteration by vol-canic gases.The depletion in δ^18O in wall rocks is controlled by the composition and nature of flu-ids,the temperature of fluids,the elevation of rocks at the time of alteration ,lithology,boiling effects of fluids ,and alteration style,as well as by water/rock ratios.In addition ,the fluids re-sponsible for epithermal deposits have experienced positive δ^18O shifts .It seems that when the above complications and controlling factors are well defined,oxygen isotope studies would be a promising and powerful exploration tool.     

Geochronology, Geochemistry, and Sr–Nd–Hf Isotopes of the Balazha Ore-Bearing Porphyries: Implications for Petrogenesis and Geodynamic Setting of Late Cretaceous Magmatic Rocks in the Northern Lhasa Block, Tibet

The study of Late Cretaceous magmatic rocks, developed as a result of magmatism and related porphyry mineralization in the northern Lhasa block, is of significance for understanding the associated tectonic setting and mineralization. This paper reports zircon chronology, zircon Hf isotope data, whole-rock Sr–Nd isotope data, and geochemistry data of Balazha porphyry ores in the northern Lhasa block. Geochemical features show that Balazha ore-bearing porphyries in the northern Lhasa block belong to high-Mg# adakitic rocks with a formation age of ~90 Ma; this is consistent with the Late Cretaceous magmatic activity that occurred at around 90 Ma in the region. The age of adakitic rocks is similar to the molybdenite Re–Os model age of the ore-bearing porphyries in the northern Lhasa block, indicating that the diagenesis and mineralization of both occurred during the same magmatism event in the Late Cretaceous. The Hf and Sr–Nd isotope data indicate that these magmatic rocks are the product of crust–mantle mixing. Differing proportions of materials involved in such an event form different types of medium-acid rocks, including ore-bearing porphyries. Based on regional studies, it has been proposed that Late Cretaceous magmatism and porphyry mineralization in the northern Lhasa block occurred during collision between the Lhasa and Qiangtang blocks.     

Quartz-Ferberite Oxygen Isotope Geothermometer and Its Geological Applications

Experiments for oxygen isotope exchange between ferberite and water were carried out and the followingequation on oxygen isotope fractionation between ferberite and water against temperature was obtained:Combining this equation with the equation of Clayton et al. (1972) on oxygen isotope fractionation be-tween quartz and water, an equation on oxygen isotope fractionation between quartz and ferberite was ob-tained:The Bigeleison-Mayer function method was used to calculate the oxygen isotope fractionation betweenquartz and ferberite. The theoretical curve obtained agrees with the experimental calibration results quite wellin the temperature range of study.The above calibrated equation has been used in 5 world famous tungsten deposits to determine their tem-peratures of formation. The results show that the temperature range for an idividual deposit determined by thisgeothermometer agrees with those obtained from fluid inclusion determination and other isotopegeothermometers.     

Oxygen isotope and REE geochemistry of metamorphic veins within the Zhoutan Group,central Jiangxi Province

Geochemical studies on REE, trace elements and oxygen isotopes from metamorphic veins and their host metasedimentary rocks in the Zhoutan Group at two localities, Xiangshan and Yihuang, in central Jiangxi Province have been conducted in this paper. The results show that the metamorphic quartz veins inherited the REE and oxygen isotope geochemical characteristics from their host rocks, suggesting that the vein-forming fluids were derived from the host rocks. Additionally, fractionation degrees of the trace element pairs Zr-Hf, Nb-Ta, Y-Ho and U-Th in the veins are different from those of their host rocks. It is also indicated that the veins are the products of the fluids. The metamorphic veins within the Zhoutan Group metasedimentary rocks were formed principally as a result of lateral diffusion of the metamorphic fluids.     

Hydromagmatic amphibole in komatiitic, tholeiitic and ferropicritic units, Abitibi greenstone belt, Ontario and Québec: evidence for Archaean wet basic and ultrabasic melts

Summary ?Detailed petrographic, electron microprobe and ion probe studies of Archaean hydromagmatic amphiboles from the Abitibi greenstone belt, Canada, yield new insights into the origin of Al-undepleted komatiitic and Al-depleted tholeiitic and ferropicritic melts. The amphiboles are present in peridotite layers and basal chill zones of thick differentiated basic and ultrabasic sills and flows, and are titanian pargasite–hastingsite in composition. They can be grouped into two petrographic types: (1) amphibole in the groundmass; and (2) amphibole-bearing melt inclusions. The groundmass amphiboles are oikocrysts, rims and interstitial grains, present in minor to major amounts. The oikocrysts host cumulus olivines (Fo_83–84) that are rounded in shape, embayed, and smaller in size. The amphibole-bearing melt inclusions are hosted in cumulus olivines (Fo_83–84 in komatiitic rocks and Fo₇₉ in tholeiitic rocks), spherical to ovoid in shape, 50–500 μm in size, and dominated modally by amphibole. The melt inclusions also contain euhedral chromite and aluminous spinel and micrometric clinopyroxene and glass, and sub-micrometric iron–nickel sulphide, chloro-apatite and ilmenite. In-situ ion probe analyses indicate the amphibole is: (1) enriched in Nb, LREE and Zr and depleted in Sr and HREE relative to primitive mantle; (2) contains up to 1–3 wt% H₂O; and (3) overall displays δD values from 50‰ to −140‰, including many values in the accepted magmatic range of −60‰ to −90‰. The petrographic relationships and geochemical compositions, and comparisons to experimental systems, indicate amphibole formation by subsolidus reaction of residual hydrous silicate melt with olivine and clinopyroxene. Some of the hydrous melt intruded and was entrapped as secondary melt inclusions within relict olivine. Rapid crystallization of the hydrous melt inclusions formed amphibole+clinopyroxene±glass±spinel or solely glass. Bulk compositions of the melt inclusions, comparisons to experimental phase equilibria, and presence of magmatic water suggest amphibole crystallisation from olivine → pyroxene residual melts with at least 2–3 wt% H₂O during rapid solidification of the host units. Adjustment for anhydrous phase crystallization (mainly olivine) suggests the initial melts contained 1–2 wt% H₂O. Such high H₂O contents and the magmatic δD compositions are consistent with the participation of H₂O in melt petrogenesis. However, most Abitibi komatiites and tholeiites lack hydromagmatic minerals, making it difficult to attribute all basic and ultrabasic melts to melting in hydrous Archaean mantle. The favoured model is that some Abitibi basic and ultrabasic melts were wet and some were dry, as well as Al-depleted or Al-undepleted. Received July 24, 2001; revised version accepted January 9, 2002     

Characteristics of carbonatites from the northern part of the Korean Peninsula: A perspective from distribution,geology and geochemistry

The present study introduces the carbonatite in the northern part of the Korean Peninsula for the first time.Recent exploration and development of the phosphorus-bearing carbonate rocks in the area have accumulated new geological data which gave us an opportunity to study origin of the carbonate rocks.We conducted geological survey,geochemical analyses of trace elements and rare earth elements,and carbon and oxygen isotope analyses for the carbonatites from Ssangryong,Pungnyon,Yongyu and Puhung districts of the northern part of the Korean Peninsula.This research confirms that the phosphorus-bearing carbonate rocks are carbonatite originating from the mantle.The studied carbonatites are distributed at the junctions of ring and linear structures or around their margins and contain a greater amount of REEs,Y,and Sr than carbonate rocks.The carbonatites in Yongyu and Puhung area show evidence that they were formed from mantle plume generated at the lower mantle and display similar fractionation characteristics to carbonatites in Barrado Itapirapua in Brazil and Kalkfeld and Ondurakorume in Namibia.REE patterns of the carbonatites are typical of carbonatites and the carbon and oxygen isotope analyses demonstrate that the carbonatites were originated from mantle.The carbonatites from the northern part of the Korean Peninsula have a great potential for sources of REE,Y,PGE(platinum group elements),copper,and gold.     

Discovery of Mass Independent Oxygen Isotopic Compositions in Superscale Nitrate Mineral Deposits from Turpan‐Hami Basin,Xinjiang, China and Its Significance

<正>The Turpan-Hami Basin in eastern Xinjiang is one of the driest regions on Earth and a premier environment to form and preserve nitrate.A large nitrate ore field in this basin was found recently.It is estimated there are about 2.5 billion tons of resources of nitrate,and the amount is as much as the Atacama Desert super-scale nitrate deposit in Chile.Nitrate is one of a few minerals with mass-independent fractionation(MIF),and the oxygen isotope MIF is an effective method to determine the source of nitrate.Theδ~(17)O,δ~(18)O of nitrate were measured by fluorination and thermal decomposition method.The date indicated that this is the first time that oxygen isotope MIF has been located in inland nitrate minerals.The results obtained by two methods are similar,⊿~(17)=δ~(17)O-0.52×δ~(18)O=12‰-17‰.The experiment and observation data proved that oxygen isotope MIF of nitrate are the result of photochemical reactions in the troposphere and stratosphere.Thus, evidence from MIF oxygen isotopic compositions indicate that long term atmospheric deposition of nitrate aerosol particles produced by photochemical reactions is the source of the deposits.