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.     

Hydrogen and Oxygen Isotope Fractionation Mechanism in the Hydrothermal System and Its Geologic Significance

The geochemical behaviors of hydrogen and oxygen isotopes in the hydrothermal system and their inher-ent relationship with the water / rock exchange are discussed in this paper In addition to the temperature con-ditions, the effective W / R ratio is another factor controlling the changes in H and O isotope compositions ofthe altered rock and hydrothermal water. Besides, the application and geological significance of the water-rockexchange theory are also discussed in the light of the H and O isotope compositions and their variation charac-teristics of the mineralizing hydrothermal water and altered rocks from several mineral deposits. Finally, abrief evolutional model of H and O istotope compositions of meteoric and magmatic hydrothermal waters in ahydrothermal system is given.     

Sulfur Isotope Fractionation in Magmatic Systems：Models of Rayleigh Distillation and Selective Flux

The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

A refined garnet - biotite Fe−Mg exchange geothermometer and its application in amphibolites and granulites

A new formulation of garnet-biotite Fe–Mg exchange thermometer has been developed through statistical regression of the reversed experimental data of Ferry and Spear. Input parameters include available thermo-chemical data for quaternary Fe–Mg–Ca–Mn garnet solid solution and for excess free energy terms, associated with mixing of Al and Ti, in octahedral sites, in biotite solid solution. The regression indicates that Fe–Mg mixing in biotite approximates a symmetrical regular solution model showing positive deviation from ideality withW _FeMg ^bi =1073±490 cal/mol. H _r and S _r for the garnet-biotite exchange equilibrium were derived to be 4301 cal and 1.85 cal respectively. The resultant thermometer gives consistent results for rocks with a much wider compositional range than can be accommodated by earlier formulations.     

Geopresure Field and Hydrocarbon Migration in Weixinan Depresion

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Geoscience for the public： Geotopes and National GeoParks in Germany

Geotopes or geological sites provide information on the evolution, structure and properties of the Earth‘s crust and on the geological past. They also represent the great variety of features that characterize a landscape, For this reason, their preservation is of special concern to geosciences. As early as in the 19th century, outstanding rock formations became important tourist sites although the modern terms ““geosites““ and ““geotourism““ were unknown. The paper describes the German initiatives on geotope conservation and the implementation of National GeoParks in Germany and their use for education and tourism.     

Isotope Fractionation in TiO2 Polymorphs (Rutile,Anatase, Brookite) Estimated from “First Principles”

Doklady Earth Sciences - Temperature relations of β-factors for 18O/16O fractionations in TiO2 polymorphs have been determined using the density functional theory:...     

Isotope Tracing and Prospecting Assessment of Gold-Silver Deposits in Zhejiang Province

Three different types of gold and silver deposits in Zhejiang Province(Huangshan gold deposit, Zhilingtou gold-silver deposit and Haoshi silver deposit) showmarked differences in lead and strontium isotopic composition, suggesting three differentsources and geneses of these deposits. The Huangshan gold deposit features low initial Srisotope ratios and low μ values or low content of radiogenic Pb and its ore-forming materialscame primarily from the upper mantle; the Zhilingtou gold-silver deposit shows high initial Srisotope ratios and high μ values or high content of radiogenic Pb and the ore-forming materialswere derived mainly from the upper crust; and the Haoshi silver deposit has its Pb and Srisotope ratios between the above two cases with the ore-forming materials stemming from boththe mantle and the crust. The characteristic Pb isotopic composition may serve as an indicatorfor prospecting for different types of ore deposits.     

The Erupting-Flow Model and Erupting-Flow Types in Yangbajain Geothermal Field in China

Erupting-flow types of geothermal wells in the Yangbajain geothermal field, China, are proposed based on internal energy of geothermal fluids and hydrogeologic-dynamic conditions of wellbore. An erupting-flow model, which is adaptable to the steaming and erupting of flow from wells in the field, has been verified by actual cases.     

Investigation of Hydrous Pyrolysis on Type-II Kerogen-bearing Source Rocks from Iran and its Application in Geochemical and Kinetic Analyses of Hydrocarbon Products

Hydrous pyrolysis (HP) practiced on type-II kerogen-bearing oil shale samples from the Sargelu Formation in the Ghali-Kuh Area, western Iran, using a specially designed apparatus was performed at different temperatures (250–350°C), with hydrocarbon generation evaluated at each temperature. For comparison, the samples subjected to Rock-Eval pyrolysis before proceeding to HP resulted in Tmax = 418°C, HI = 102, and TOC = 4.33%, indicating immaturity and hence remarkable hydrocarbon (especially oil) generation potential, making them appropriate for HP. Moreover, the samples were deposited in a low-energy reductive marine environment, with maximum oil and gas generation (739 mg and 348 mg out of 50 g of rock sample, respectively) observed at 330°C and 350°C, respectively. The oil generated at 330°C was subjected to gas chromatography (GC) and isotopic analyses to assess hydrocarbon quality and composition. The hydrocarbon generation data was devised to estimate kinetic indices of the Arrhenius equation and to investigate the gas–oil ratio (GOR) and overall conversion yield. Based on the producible hydrocarbon quantity and quality, the findings contribute to the economic assessment of oil shales across the study area. The developed kinetic model indicates the history of hydrocarbon generation and organic matter (OM) maturity.     

Isotope Geochemical Characteristics and Material Sources of Tin--Bearing Porphyries in South China

Tin-bearing porphyries in South China can be divided into the F-rich and F-poorsubtypes. They are high-silica (SiO_2>71%), peraluminous (A/NKC>1.0) and rich inincompatible elements (Rb, Zr, U, W, Sn) and have weak Ce (δCe=0.68-0.82) and strong Eu(δEu=0.01-0.38) negative anomalies. Meantime, they also have low δ_(Nd)(-6.3- -8.4), high~(207)Pb/~(204)Pb (15.588-15.790), medium to high (~(87)Sr/~(86)Sr)_i (0.7084-0.7287) and relatively highδ~(18)O(9.1-10.3‰). These characteristics clearly suggest that the two subtypes of tin-bearingporphyries were derived from the crustal materials. Their differences lie only in the existence ofcertain different components in their source materials. Therefore, there is only one type oftin-bearing prophyry in South China. that is continental crust transformation type.     

Present-day Upper-crustal Strain Rate Field in Southeastern Tibet and its Geodynamic Implications: Constraints from GPS Measurements with ABIC Method

The Earth’s surface kinematics and deformation are fundamental to understanding crustal evolution. An effective research approach is to estimate regional motion field and deformation fields based on modern geodetic networks. If the discrete observed velocity field is obtained, the velocity related fields, such as dilatation rate and maximum shear strain rate, can be estimated by applying varied mathematical approaches. This study applied Akaike''s Bayesian Information Criterion (ABIC) method to calculate strain rate fields constrained by GPS observations in the southeast Tibetan Plateau. Comparison with results derived from other three methods revealed that our ABIC-derived strain rate fields were more precise. The maximum shear strain rate highlighted the Xianshuihe–Xiaojiang fault system as the main boundary for the outward migration of material in southeastern Tibet, indicating rotation of eastern Tibet material around the eastern Himalaya rather than whole extrusion along a fixed channel. Additionally, distinct dilatation rate patterns in the northeast and southwest regions of the fault system were observed. The northeast region, represented by the Longmenshan area, exhibited negative dilatational anomalies; while the southwest region, represented by the Jinsha River area north of 29°N, displayed positive dilatational anomalies. This indicates compression in the former and extension in the latter. Combined with deep geophysical observations, we believe that the upper and lower crusts of the Jinsha River area north of 29°N are in an entire expanding state, probably caused by the escape-drag effect of material. The presence of a large, low-viscosity region south of 29°N may not enable the entire escape of the crust, but instead result in a differential escape of the lower crust faster than the upper crust.     

Isotope Geochemistry of the Dongchuan Copper Deposit,Yunnan,SW China： Stratigraphic Chronology and Application of Lead Isotopes in Geochemical Exploration

In this paper the Pb-Pb isochron method was used to determine the isotopic ages of the Luoxue Formation dolomites (1716 ±56 Ma), the Heishan Formation carbonaceous slates ( 1607 ±128 Ma) of the middle sub-group of the Kunyang Group and the Dayingpan Formation carbonaceous slates (1258 ±70Ma) of the upper sub-group of the Kunyang Group. The age of the middle sub-group of the Kunyang Group is about 1800 – 1600 Ma, belonging to the Late Paleo-Proterozoic, and that of the Dayingpan Formation in the upper sub-group of the Kunyang Group is about 1200 – 1300 Ma, belonging to the Middle Proterozoic. In addition, the Pb isotope chemical exploration techniques were used to study systematically the Pb isotopic compositions of rocks and ores across the No. 14 vein in the middle segment of the No. 1 pit of the Tangdan copper deposit and the result showed that the Pb isotope V₁ values are negatively correlated with the copper contents. It is the first trial to use the systematic section method to conduct Pb isotope chemical exploration. This research project was financially supported jointly by the National Natural Science Foundation of China (Grant Nos. 49702022, 40073001) and the State 973 Program (No.G1999043215).     

Sulphur and Lead Isotope Compositions of the Dajiangping Deposit in Western Guangdong Province

The Dajiangping pyrite deposit located in the middle sector of the Yunkai uplift in western Guangdong is a stratiform sulphide deposit occurring in Sinian marine clastic and fine clastic rocks. The formation of the deposit was related to submarine exhalation and hot brine deposition. A part of it was reformed by late-stage hydrothermal solution. The δ34S values of pyrite vary from - 25.55‰ to +21.07‰, which are inversely proportional to the content of organic carbon in ore and pyrite. Passing from striped fine-grained pyrite ore to massive coarse-grained pyrite ore, i.e. from south to north, the sulphur isotopic composition changes from the light sulphur-enriched one to the heavy sulphur-enriched one. The lead isotopic composition of striped ore is consistent with that of the country rocks of orebodies and the lead is radiogenic lead derived from the upper crust. The lead isotopic composition of massive ore is relatively homogeneous and its 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios are a bit lo     

Carbon and Oxygen Isotope Compositions of Some Upper Cretaceous–Paleocene Sequences in Argentina and Chile

The Cretaceous-Paleocene (K-T) transition has been recorded in sedimentary carbonate rocks in northwestern Argentina and southern Chile. In the Yacoraite Basin, Argentina, this transition has been preserved in a 2 m thick marly layer, at the base of the Tunal Formation, which overlies lacustrine/marine carbonates of the Yacoraite Formation (Cabra Corral dam). The K-T transition is also preserved at Maimara, where Tertiary sandstones overlie a 50 m thick limestone bed of the Yacoraite Formation. In the Magellan Basin, Chile, glauconitic sandstones with calcitic cement and limestone concretions of the Maastrichtian Punta Rocallosa Formation are overlain by sandstones, claystones, and limestones of the Chorillo Chico Formation. The K-T transition is preserved in the lower portion of the Chorillo Chico Formation.

Carbonates of the Yacoraite Formation display bulk-rock δ¹³C values from +1 to +2‰ PDB, with a negative incursion (?4‰ PDB) at the K-T transition. δ¹³C values in the Tunal Formation marls vary from ?3 to ?1‰ PDB. At Rocallosa Point, δ¹³C values in limestone strata, calcite cement, and limestone concretions vary from ?4 to ?33 ‰ PDB, and the lowest value in the Chorillo Chico Formation apparently marks the K-T transition. The δ¹⁸O fluctuations in the Yacoraite and Magellan carbonate rocks suggest a temperature drop at the K-T transition, followed by a temperature rise.

High ⁸⁷Sr/⁸⁶Sr ratios (0.7140-0.7156) characterize the studied profiles of the Yacoraite Formation, documenting an important ⁸⁷Sr-enriched source of Sr to the water from which these carbonates precipitated. At the Magellan basin, ⁸⁷Sr/⁸⁶Sr ratios are closer to the expected values for the global Late Cretaceous-Paleocene ocean.     

Study of structural and valence state of Cr and Fe in chrysoberyl and alexandrite with EPR and M?ssbauer spectroscopy

Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given. It is shown that the Cr³⁺ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site. During the annealing of the alexandrite crystals, Cr³⁺ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution of different valence Fe ions. The various proportions of both Fe²⁺ and Fe³⁺ ions isomorphically entering the octahedral sites in the BeAl₂O₄ crystal structure were established.