Oxygen isotope (δ18O) serves as paleothermometer, and provides paleotemperature for carbonates. δ18O signature was used to estimate the temperature of fractionation of dolomite and calcite in Montney Formation, empi...Oxygen isotope (δ18O) serves as paleothermometer, and provides paleotemperature for carbonates. δ18O signature was used to estimate the temperature of fractionation of dolomite and calcite in Montney Formation, empirically calculated to have precipitated, between approximately 13°C to ±33°C during Triassic time in northeastern British Columbia, Western Canada Sedimentary Basin (WCSB). Measurements of stable isotopes (δ13C and δ18O) fractionation, supported by quantitative X-ray diffraction evidence, and whole-rock geochemical characterization of the Triassic Montney Formation indicates the presence of calcite, dolomite, magnesium, carbon and other elements. Results from isotopic signature obtained from bulk calcite and bulk dolomite from this study indicates depleted δ13CPDB (-2.18‰ to -8.46‰) and depleted δ18OPDB (-3.54‰ to -16.15‰), which is interpreted in relation to oxidation of organic matter during diagenesis. Diagenetic modification of dolomitized very fine-grained, silty-sandstone of the Montney Formation may have occurred in stages of progressive oxidation and reduction reactions involving chemical elements such as Fe, which manifest in mineral form as pyrite, particularly, during early burial diagenesis. Such mineralogical changes evident in this study from petrography and SEM, includes cementation, authigenic quartz overgrowth and mineral replacement involving calcite and dolomite, which are typical of diagenesis. High concentration of chemical elements in the Montney Formation?-Ca and Mg indicates dolomitization. It is interpreted herein, that calcite may have been precipitated into the interstitial pore space of the intergranular matrix of very fine-grained silty-sandstone of the Montney Formation as cement by a complex mechanism resulting in the interlocking of grains.展开更多
To explain the presence and spatial distribution of NO_(3)^(−)and N-NH_(3)in the Aquifer of the Metropolitan Area of Mexico City(AMAMC),a hydrogeochemical and isotopic analysis using^(13)C DIC(as well as the stable is...To explain the presence and spatial distribution of NO_(3)^(−)and N-NH_(3)in the Aquifer of the Metropolitan Area of Mexico City(AMAMC),a hydrogeochemical and isotopic analysis using^(13)C DIC(as well as the stable isotopes^(18)O and^(2)H)in groundwater was conducted.This aquifer is located in an old closed lacustrine volcano-sedimentary basin;some wells hosted in the semi-confined zone contain high N-NH_(3)concentrations,while others present NO_(3)^(−)contents in the recharge zones(hosted in an oxidizing environment).In this study,a change in the isotopic signature(primarily in^(18)O and^(2)H)was observed from the recharge zones to the basin center in some of the wells with high NO_(3)^(−)concentrations,this behavior can be attributed to evaporation during the incorporation of recently infiltrated water.In addition,the results for^(13)C(along with ^(2) H)in wells with the highest N-NH_(3)concentrations exhibited an atypically broad range of values.Results indicated the occurrence of hydrogeochemical and/or biochemical processes in the aquifer(in an oxidizing or reducing environment),such as organic degradation,bacterial decomposition(primarily in the ancient Lake Texcoco and which acts as a natural sink for carbon,nitrogen,sulfur,and phosphorus),besides rock weathering and dissolution,which may be responsible for a very marked isotopic modification of the^(13)C(and,to a lesser extent,2 H).Methanotrophic bacterial activity and methanogenic activity may be related to N-NH_(3)removal processes by oxidation and residual water incorporation respectively,whereas the increase in the NO_(3)^(−)content in some wells is due to the recent contribution of poor-quality water due to contamination.展开更多
The Laojiezi alkaline volcanic rocks, which are located in the intraplate region of the Yangtze craton, coincide with the formation of the Jinshajiang-Ailaoshan-Red River alkaline rock belt. Although this belt has bee...The Laojiezi alkaline volcanic rocks, which are located in the intraplate region of the Yangtze craton, coincide with the formation of the Jinshajiang-Ailaoshan-Red River alkaline rock belt. Although this belt has been widely studied by geologists because of its porphyry-related Pb-Ag-Au polymetallic deposit and geotectonic location, the material sources of this belt are still debate. Whole-rock analyses show that these rocks have high total alkali contents(3.73–11.08 wt%), and their aluminum saturation index(ASI) values widely vary from 0.82 to 3.07, which comprise a metaluminous-peraluminous magma series. These rocks are characterized by high K(K2 O/Na2 O>1) and low Ti and Mg contents; enrichment in large-ion lithophile elements, such as Rb, Ba, K and light rare earth elements; and depletion in high field strength elements, such as Ta, Nb, P, and Ti. These rocks exhibit moderate Eu(Eu/Eu*=0.86–1.04) and Ce(Ce/Ce*=0.63–0.96) anomalies. Their(87 Sr/86 Sr)i, εNd(t), zircon εHf(t) and δ18 O values range from 0.70839 to 0.71013, from-10.16 to-12.45, from-19.6 to-5.8, and from 5.69‰ to 8.54‰, respectively, and their Nd and Hf two-stage model ages(TDM2) are 1.67–1.86 Ga and 1.27–2.02 Ga, respectively. These data reflect the primary partial melting of Paleoproterozoic to Mesoproterozoic lower crust with minor residual continental lithospheric mantle and supracrustal metasediments. The lithosphere was likely thickened along the southeastern margin of the Tibetan Plateau following the Indian-Asian continentcontinent collision(65–41 Ma). During the post-collision phase(36–16 Ma), the transition from a compressional to extensional setting triggered the convective removal of the over-thickened CLM beneath the Yangtze craton, which led to the upwelling of asthenospheric materials. This process created alkali-rich and high-K magma through the partial melting of the thickened lower crust. Magma that carried Cu-Au-Pb-Ag minerals was emplaced by strike-slip motion along the E-to W-or ENE-to WSWtrending tectonically weak zone, finally forming an alkaline porphyry Cu-Au-Pb-Ag polymetallic deposit.展开更多
Geologic, petrographic and petrochemical studies of the late Mesozoic K-rich melanocratic dykes, including lamprophyres, andesite porphyrites and dacite-porphyry in the gold field system in the Jiaodong Peninsula, Chi...Geologic, petrographic and petrochemical studies of the late Mesozoic K-rich melanocratic dykes, including lamprophyres, andesite porphyrites and dacite-porphyry in the gold field system in the Jiaodong Peninsula, China, have shown that these dykes are characterized by rich potassium and alkali but poor titanium. They belong to an ultra-high potassic, shoshonitic and high potassic calc-alkaline rock series. The parental magma has relatively high initial strontium ratios ((87Sr/86Sr),=0.70895-0.71140) and low (143Nd/144Nd)1 ratios (varying from 0.51135 to 0.51231); and its δ18Osmow, whole rock values vary from +5.8%c to +10.6%c with a mean of +7.1%c. These features suggest that the source region of the magma is an enriched mantle wedge transformed from a continental lithosphere mantle which has experienced metasomatism by mantle-derived fluids with H2O-dominated fluids that were provided during the underthrusting of an ocean crust. The initial magma was generated by low-degree partial melting of the enriched mantle in its mature stage in the back-arc spreading environment. The evolution of magmas is associated with two trends, i.e., fractional crystallization and mixing with or intensive contamination by palaeo-crust materials or metamorphic rocks. The former process is evident in the gold field system of quartz-vein type, whereas the latter is dominated in the gold field system of the altered-rock type. This conclusion is very important for more detailed study of petrogenesis and mineralization through the crust-mantle interaction (exchange) in the Mesozoic in this region.展开更多
Aptian is characterized by widespread deposition of organic-rich sediment.The Aptian bitumen limestone horizon,which is thin decimetre-thick sequences,locally crops out in the Kircaova area,Eastern Black Sea Region(Ea...Aptian is characterized by widespread deposition of organic-rich sediment.The Aptian bitumen limestone horizon,which is thin decimetre-thick sequences,locally crops out in the Kircaova area,Eastern Black Sea Region(Eastern Pontides).They are well correlated with Aptian bitumen limestone in the other Tethys Reams.They are proposed as episodes of increased organic matter.However,background factors controlling organic matter enrichment are poorly known.In this study,we present new inorganic geochemistry,including trace elements,rare earth elements(REE),redox-sensitive elements(RSE),stable-isotopes(δ~(18)O andδ~(13)C),and total organic carbon(TOC).We integrated new geochemical data with existing stratigraphy,paleontology,and organic chemistry data to provide new insight into the depositional environment and paleoclimate conditions during Aptian.The lacustrine bitumen limestone(LBL)samples have variedδ~(13)C(ave.-1.45‰)andδ~(18)O(ave.-4.50‰).They possess distinct REE patterns,with an average of REE(ave.14.45 ppm)and Y/Ho(ave.35)ratios.In addition,they have variable Nd/YbN(0.28-0.81;ave.0.56)and Ce/Ce*(0.68-0.97;ave.0.86),and relatively high Eu^(*)/Eu(1.23-1.53;ave.1.35).They display seawater signatures with reduced oxygen conditions.The enrichment in RSE(Mo,Cu,Ni,and Zn)and the low Mo/TOC(0.70-3.69;ave.2.41)support a certain degree of water restriction.The high Sr/Ba,Sr/Cu,Ga/Rb,and K/Al records of the LBL facies suggest hot house climatic conditions.The sedimentary environment was probably an isolated basin that is transformed from the marine basin.In addition to depositional conditions,the regional parameters such as the climate,increased run-off period,nutrient levels,alkalinity level,and dominant carbonate producers favored the enrichment in organic matter of LBL facies.Thus,extreme greenhouse palaeoclimate conditions have an important role in organic matter enrichment in the isolated basin.Our results are conformable with the published data from marine,semi-restricted basin,and lacustrine settings in the different parts of the Tethys margin.Thus,this approach provides the first insight into the Aptian greenhouse paleo-climate conditions of the Eastern Black Sea Region,NE Turkey.展开更多
In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation an...In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and S7Sr/S6Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than -5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate- derived, with the δ13C generally more than -2.0‰PDB, 18δO less than -10.0‰PDB, Z value more than 120 and STSr/S6Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid （including possibly a little mantle-derived fluid or meteoric water）, with the j13C generally ranging from -2.0‰ to -8.0‰PDB, δ18O from -10.0‰ to -18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to -10.0‰PDB, δ18O less than -8.0%rPDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.展开更多
Stable carbon isotope geochemistry provides important information for the recognition of funda- mental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elab- oration of m...Stable carbon isotope geochemistry provides important information for the recognition of funda- mental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elab- oration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon （organic matter, mantle, or carbonates） and help to constrain the fluid history and the mechanisms involved in graphite deposition. Graphite precipitation in fluid-deposited occurrences results from C02- and/or CH4-bearing aqueous fluids. Fluid flow can be considered as both a closed （without replenishment of the fluid） or an open system （with renewal of the fluid by successive fluid batches）. In closed systems, carbon isotope systematics in graphite is mainly governed by Rayleigh precipi- tation and/or by changes in temperature affecting the fractionation factor between fluid and graphite. Such processes result in zoned graphite crystals or in successive graphite generations showing, in both cases, isotopic variation towards progressive 13C or 12C enrichment （depending upon the dominant carbon phase in the fluid, C02 or CH4, respectively）. In open systems, in which carbon is episodically introduced along the fracture systems, the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of 613C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.展开更多
Power-law patterns appear in a variety of natural systems on the modern Earth;nevertheless,whether such behaviors appeared in the deep-time environment has rarely been studied. Isotopic records in sedimentary rocks, w...Power-law patterns appear in a variety of natural systems on the modern Earth;nevertheless,whether such behaviors appeared in the deep-time environment has rarely been studied. Isotopic records in sedimentary rocks, which are widely used to reconstruct the geological/geochemical conditions in paleoenvironments and the evolutionary trajectories of biogeochemical cycles, offer an opportunity to investigate power laws in ancient geological systems. In this study, I focus on the Phanerozoic sedimentary records of carbon, oxygen, sulfur, and strontium isotopes, which have well documented and extraordinarily comprehensive datasets. I perform statistical analyses on these datasets and show that the variations in the sedimentary records of the four isotopes exhibit power-law behaviors. The exponents of these power laws range between 2.2 and 2.9;this narrow interval indicates that the variations in carbon, oxygen, sulfur, and strontium isotopes likely belong to the same universality class, suggesting that these systematic power-law patterns are governed by universal, scale-free mechanisms. I then derive a general form for these power laws from a minimalistic model based on basic physical principles and geosystem-specific assumptions, which provides an interpretation for the power-law patterns from the perspective of thermodynamics. The fundamental mechanisms regulating such patterns might have been ubiquitous in paleoenvironments, implying that similar power-law behaviors may exist in the sedimentary records of other isotopes.展开更多
Nd, Sr and O isotopic study on the spilite-keratophyre sequence in Xiqiu shows that its ∈_(Nd) values are inthe range of 4.02-5.26, and its ∈_(Sr) values, +1.4-2.6. According to the points of these data in the ∈_(N...Nd, Sr and O isotopic study on the spilite-keratophyre sequence in Xiqiu shows that its ∈_(Nd) values are inthe range of 4.02-5.26, and its ∈_(Sr) values, +1.4-2.6. According to the points of these data in the ∈_(Nd)-T,∈_(Sr)-T and ∈_(Nd)-∈_(Sr) diagrams, the spilite-keratophyre is interpreted as being slightly contaminated by crustalmaterials. Its δ^(18)O values are 3.9-5.0‰. The depletion of ^(18)O in the rocks resulted from the influence ofseawater hydrothermal alteration during or soon after the rock formation. Based on the isotopic characteristicsand available geochemical data, it is believed that the spilite-keratophyre was formed in the well-developedisland-arc environment during the Late Proterozoic subduction of the palaeo-Pacific plate beneath thesoutheastern margin of the Yangtze massif.展开更多
The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-tren...The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD（H2O-SMOW） and δ18O（H2O-SMOW） values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ13C（PDB） values ranging from-6.2‰ to-4.1‰ and δ18O（SMOW） values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ34S（CDT） values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The 206Pb/204Pb,207Pb/204Pb and 208Pb/204Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.展开更多
This paper focuses on the effect of the later hydrotherm on uraniferous leucogranites and the stages of uranium mineralization. Here, we review C-H-O stable isotope, elements and fluid geochemistry of uraniferous leuc...This paper focuses on the effect of the later hydrotherm on uraniferous leucogranites and the stages of uranium mineralization. Here, we review C-H-O stable isotope, elements and fluid geochemistry of uraniferous leucogranites in Gaudeanmus, Namibia. The results show that there is significant increasing amount of rare earth element from non-mineralized to uraniferous leucogra-nites, indicating the synchronization of REE enrichment and uranium mineralization. Uranium enrichment may have close relations with Pb, Th, Co, Ni, REE in this region, so REE and U evidently exist homology. There are at least two stages of uranium mineralization by later hydrothermal alteration: firstly, due to magnatic residual high temperature and low salinity fluid, the temperature of main metallogenetic epoch ranges from 470°C to 530°C, salinity ranges from 3.55% to 9.60% NaCleq, and C, H, O stable isotope is -23‰ - -13.6‰, -53.3‰ - -46.4‰, 7.71‰ - 8.81‰, respectively. Secondly, due to superim-posed hydrothermal fluid, the temperature, salinity, and C, H, O stable isotope is 150°C - 220°C, 4.65% - 19.05% NaCleq, -20.3‰ -?-3.7‰, -64.7‰ - -53.6‰, 1.49‰ - 1.99‰, respectively. The fluid for reformation is derived from postmagmatic fluid, mixed with a number of meteoric water.展开更多
The Gejiu-Bozushan-Laojunshan W-Sn polymetallic metallogenic belt(GBLB)in southeast Yunnan Province is an important part of the southwestern Yangtze Block in South China.Tin polymetallic mineralization in this belt in...The Gejiu-Bozushan-Laojunshan W-Sn polymetallic metallogenic belt(GBLB)in southeast Yunnan Province is an important part of the southwestern Yangtze Block in South China.Tin polymetallic mineralization in this belt includes the Niusipo,Malage,Songshujiao,Laochang and Kafang ore fields in the Gejiu area which are spatially and temporally associated with the Kafang-Laochang and Songshujiao granite plutons.These granites are characterized by variable A/CNK values(mostly>1.1,except for two samples with 1.09),high contents of SiO2(74.38-76.84 wt.%)and Al2 O3(12.46-14.05 wt.%)and variable CaO/Na2 O ratios(0.2-0.65)as well as high zirconδ18O values(7.74‰-9.86‰),indicative of S-type affinities.These rocks are depleted in Rb,Th,U,Ti,LREE[(La/Yb)N=1.4-20.51],Ba,Nb,Sr,and Ti and display strong negative Eu and Ba anomalies.The rocks possess high Rb/Sr and Rb/Ba ratios,relatively low initial 87Sr/86Sr ratios(0.6917-0.7101),and less radiogenicεNd(t)values(-8.0 to-9.1).The zircon grains from these rocks show negativeεHf(t)values in the range of-3.7 to-9.9 with mean TDM2(Nd)and TDM2(Hf)values of 1.57 Ga and 1.55 Ga.They show initial 207Pb/204Pb ranging from15.69 to 15.71 and 206Pb/204Pb from 18.36 to 18.70.Monazite from Songshujiao granites exhibits higher U and lower Th/U ratios,lowerδ18O values and higherεHf(t)values than those of the zircon grains in the KafangLaochang granites.The geochemical and isotopic features indicate that the Laochang-Kafang granites originated by partial melting of Mesoproterozoic crustal components including biotite-rich metapelite and metagraywacke,whereas the Songshujiao granites were derived from Mesoproterozoic muscovite-rich metapelite crustal source.Most zircon grains from the Songshujiao,Laochang and Kafang granites have high-U concentrations and their SIMS U-Pb ages show age scatter from 81.6 Ma to 88.6 Ma,80.7 Ma to 86.1 Ma and 82.3 Ma to 87.0 Ma,suggesting formation earlier than the monazite and cassiterite.Monazite SIMS U-Pb ages and Th-Pb ages of three same granite samples are consistent and show yielded 206 Pb/238U ages of 83.7±0.6 Ma,83.7±0.6 Ma,and 83.4±0.6 Ma,and 208Pb/232Th ages of 83.2±0.5 Ma,83.8±0.4 Ma,and 83.5±0.9 Ma,which are within the range of the SIMS zircon U-Pb ages from these rocks.The data constrain the crystallization of the granites at ca.83 Ma.In situ U-Pb dating of two cassiterite samples from the cassiterite-sulfide ore in the Songshujiao ore field and Kafang ore field,and two from the cassiterite-oxide+cassiterite bearing dolomite in the Laochang ore field yielded weighted mean 206 Pb/238U ages of 83.5±0.4 Ma(MSWD=0.6),83.5±0.4 Ma(MSWD=0.5),83.6±0.4 Ma(MSWD=0.6)and 83.2±0.7 Ma(MSWD=0.6),respectively.Combined with geological characteristics,the new geochronological data indicate that the formation of the granites and Sn polymetallic deposits are coeval.We correlate the magmatic and metallogenic event with lithospheric thinning and asthenosphere upwelling in continental extension setting in relation to the eastward subduction of the Neo-Tethys beneath the Sanjiang tectonic domain during Late Cretaceous.展开更多
A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor lo...A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.展开更多
The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million ton...The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.展开更多
文摘Oxygen isotope (δ18O) serves as paleothermometer, and provides paleotemperature for carbonates. δ18O signature was used to estimate the temperature of fractionation of dolomite and calcite in Montney Formation, empirically calculated to have precipitated, between approximately 13°C to ±33°C during Triassic time in northeastern British Columbia, Western Canada Sedimentary Basin (WCSB). Measurements of stable isotopes (δ13C and δ18O) fractionation, supported by quantitative X-ray diffraction evidence, and whole-rock geochemical characterization of the Triassic Montney Formation indicates the presence of calcite, dolomite, magnesium, carbon and other elements. Results from isotopic signature obtained from bulk calcite and bulk dolomite from this study indicates depleted δ13CPDB (-2.18‰ to -8.46‰) and depleted δ18OPDB (-3.54‰ to -16.15‰), which is interpreted in relation to oxidation of organic matter during diagenesis. Diagenetic modification of dolomitized very fine-grained, silty-sandstone of the Montney Formation may have occurred in stages of progressive oxidation and reduction reactions involving chemical elements such as Fe, which manifest in mineral form as pyrite, particularly, during early burial diagenesis. Such mineralogical changes evident in this study from petrography and SEM, includes cementation, authigenic quartz overgrowth and mineral replacement involving calcite and dolomite, which are typical of diagenesis. High concentration of chemical elements in the Montney Formation?-Ca and Mg indicates dolomitization. It is interpreted herein, that calcite may have been precipitated into the interstitial pore space of the intergranular matrix of very fine-grained silty-sandstone of the Montney Formation as cement by a complex mechanism resulting in the interlocking of grains.
基金support granted to carry out the research,and for the funding,Dr.Graciela Herrera Zamarron,responsible for the project with Contract number 0266-1O-ED-F-DGAT-UNAM-2-19-1928.
文摘To explain the presence and spatial distribution of NO_(3)^(−)and N-NH_(3)in the Aquifer of the Metropolitan Area of Mexico City(AMAMC),a hydrogeochemical and isotopic analysis using^(13)C DIC(as well as the stable isotopes^(18)O and^(2)H)in groundwater was conducted.This aquifer is located in an old closed lacustrine volcano-sedimentary basin;some wells hosted in the semi-confined zone contain high N-NH_(3)concentrations,while others present NO_(3)^(−)contents in the recharge zones(hosted in an oxidizing environment).In this study,a change in the isotopic signature(primarily in^(18)O and^(2)H)was observed from the recharge zones to the basin center in some of the wells with high NO_(3)^(−)concentrations,this behavior can be attributed to evaporation during the incorporation of recently infiltrated water.In addition,the results for^(13)C(along with ^(2) H)in wells with the highest N-NH_(3)concentrations exhibited an atypically broad range of values.Results indicated the occurrence of hydrogeochemical and/or biochemical processes in the aquifer(in an oxidizing or reducing environment),such as organic degradation,bacterial decomposition(primarily in the ancient Lake Texcoco and which acts as a natural sink for carbon,nitrogen,sulfur,and phosphorus),besides rock weathering and dissolution,which may be responsible for a very marked isotopic modification of the^(13)C(and,to a lesser extent,2 H).Methanotrophic bacterial activity and methanogenic activity may be related to N-NH_(3)removal processes by oxidation and residual water incorporation respectively,whereas the increase in the NO_(3)^(−)content in some wells is due to the recent contribution of poor-quality water due to contamination.
基金funded by the Open Foundation of the Beijing SHRIMP Center (DDC15-016)the Applied Basic Research Program Youth Project of Yunnan Province (2016DF031)the National Basic Research Program of China (2015CB452605)
文摘The Laojiezi alkaline volcanic rocks, which are located in the intraplate region of the Yangtze craton, coincide with the formation of the Jinshajiang-Ailaoshan-Red River alkaline rock belt. Although this belt has been widely studied by geologists because of its porphyry-related Pb-Ag-Au polymetallic deposit and geotectonic location, the material sources of this belt are still debate. Whole-rock analyses show that these rocks have high total alkali contents(3.73–11.08 wt%), and their aluminum saturation index(ASI) values widely vary from 0.82 to 3.07, which comprise a metaluminous-peraluminous magma series. These rocks are characterized by high K(K2 O/Na2 O>1) and low Ti and Mg contents; enrichment in large-ion lithophile elements, such as Rb, Ba, K and light rare earth elements; and depletion in high field strength elements, such as Ta, Nb, P, and Ti. These rocks exhibit moderate Eu(Eu/Eu*=0.86–1.04) and Ce(Ce/Ce*=0.63–0.96) anomalies. Their(87 Sr/86 Sr)i, εNd(t), zircon εHf(t) and δ18 O values range from 0.70839 to 0.71013, from-10.16 to-12.45, from-19.6 to-5.8, and from 5.69‰ to 8.54‰, respectively, and their Nd and Hf two-stage model ages(TDM2) are 1.67–1.86 Ga and 1.27–2.02 Ga, respectively. These data reflect the primary partial melting of Paleoproterozoic to Mesoproterozoic lower crust with minor residual continental lithospheric mantle and supracrustal metasediments. The lithosphere was likely thickened along the southeastern margin of the Tibetan Plateau following the Indian-Asian continentcontinent collision(65–41 Ma). During the post-collision phase(36–16 Ma), the transition from a compressional to extensional setting triggered the convective removal of the over-thickened CLM beneath the Yangtze craton, which led to the upwelling of asthenospheric materials. This process created alkali-rich and high-K magma through the partial melting of the thickened lower crust. Magma that carried Cu-Au-Pb-Ag minerals was emplaced by strike-slip motion along the E-to W-or ENE-to WSWtrending tectonically weak zone, finally forming an alkaline porphyry Cu-Au-Pb-Ag polymetallic deposit.
文摘Geologic, petrographic and petrochemical studies of the late Mesozoic K-rich melanocratic dykes, including lamprophyres, andesite porphyrites and dacite-porphyry in the gold field system in the Jiaodong Peninsula, China, have shown that these dykes are characterized by rich potassium and alkali but poor titanium. They belong to an ultra-high potassic, shoshonitic and high potassic calc-alkaline rock series. The parental magma has relatively high initial strontium ratios ((87Sr/86Sr),=0.70895-0.71140) and low (143Nd/144Nd)1 ratios (varying from 0.51135 to 0.51231); and its δ18Osmow, whole rock values vary from +5.8%c to +10.6%c with a mean of +7.1%c. These features suggest that the source region of the magma is an enriched mantle wedge transformed from a continental lithosphere mantle which has experienced metasomatism by mantle-derived fluids with H2O-dominated fluids that were provided during the underthrusting of an ocean crust. The initial magma was generated by low-degree partial melting of the enriched mantle in its mature stage in the back-arc spreading environment. The evolution of magmas is associated with two trends, i.e., fractional crystallization and mixing with or intensive contamination by palaeo-crust materials or metamorphic rocks. The former process is evident in the gold field system of quartz-vein type, whereas the latter is dominated in the gold field system of the altered-rock type. This conclusion is very important for more detailed study of petrogenesis and mineralization through the crust-mantle interaction (exchange) in the Mesozoic in this region.
文摘Aptian is characterized by widespread deposition of organic-rich sediment.The Aptian bitumen limestone horizon,which is thin decimetre-thick sequences,locally crops out in the Kircaova area,Eastern Black Sea Region(Eastern Pontides).They are well correlated with Aptian bitumen limestone in the other Tethys Reams.They are proposed as episodes of increased organic matter.However,background factors controlling organic matter enrichment are poorly known.In this study,we present new inorganic geochemistry,including trace elements,rare earth elements(REE),redox-sensitive elements(RSE),stable-isotopes(δ~(18)O andδ~(13)C),and total organic carbon(TOC).We integrated new geochemical data with existing stratigraphy,paleontology,and organic chemistry data to provide new insight into the depositional environment and paleoclimate conditions during Aptian.The lacustrine bitumen limestone(LBL)samples have variedδ~(13)C(ave.-1.45‰)andδ~(18)O(ave.-4.50‰).They possess distinct REE patterns,with an average of REE(ave.14.45 ppm)and Y/Ho(ave.35)ratios.In addition,they have variable Nd/YbN(0.28-0.81;ave.0.56)and Ce/Ce*(0.68-0.97;ave.0.86),and relatively high Eu^(*)/Eu(1.23-1.53;ave.1.35).They display seawater signatures with reduced oxygen conditions.The enrichment in RSE(Mo,Cu,Ni,and Zn)and the low Mo/TOC(0.70-3.69;ave.2.41)support a certain degree of water restriction.The high Sr/Ba,Sr/Cu,Ga/Rb,and K/Al records of the LBL facies suggest hot house climatic conditions.The sedimentary environment was probably an isolated basin that is transformed from the marine basin.In addition to depositional conditions,the regional parameters such as the climate,increased run-off period,nutrient levels,alkalinity level,and dominant carbonate producers favored the enrichment in organic matter of LBL facies.Thus,extreme greenhouse palaeoclimate conditions have an important role in organic matter enrichment in the isolated basin.Our results are conformable with the published data from marine,semi-restricted basin,and lacustrine settings in the different parts of the Tethys margin.Thus,this approach provides the first insight into the Aptian greenhouse paleo-climate conditions of the Eastern Black Sea Region,NE Turkey.
基金supported by the National Basic Research Project("973" Project,Grant No. 2006CB202305) and SINOPEC
文摘In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and S7Sr/S6Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than -5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate- derived, with the δ13C generally more than -2.0‰PDB, 18δO less than -10.0‰PDB, Z value more than 120 and STSr/S6Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid （including possibly a little mantle-derived fluid or meteoric water）, with the j13C generally ranging from -2.0‰ to -8.0‰PDB, δ18O from -10.0‰ to -18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to -10.0‰PDB, δ18O less than -8.0%rPDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.
基金contribution from project CGL2010-16008 (Spanish Ministry for Science and Innovation)
文摘Stable carbon isotope geochemistry provides important information for the recognition of funda- mental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elab- oration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon （organic matter, mantle, or carbonates） and help to constrain the fluid history and the mechanisms involved in graphite deposition. Graphite precipitation in fluid-deposited occurrences results from C02- and/or CH4-bearing aqueous fluids. Fluid flow can be considered as both a closed （without replenishment of the fluid） or an open system （with renewal of the fluid by successive fluid batches）. In closed systems, carbon isotope systematics in graphite is mainly governed by Rayleigh precipi- tation and/or by changes in temperature affecting the fractionation factor between fluid and graphite. Such processes result in zoned graphite crystals or in successive graphite generations showing, in both cases, isotopic variation towards progressive 13C or 12C enrichment （depending upon the dominant carbon phase in the fluid, C02 or CH4, respectively）. In open systems, in which carbon is episodically introduced along the fracture systems, the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of 613C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.
文摘Power-law patterns appear in a variety of natural systems on the modern Earth;nevertheless,whether such behaviors appeared in the deep-time environment has rarely been studied. Isotopic records in sedimentary rocks, which are widely used to reconstruct the geological/geochemical conditions in paleoenvironments and the evolutionary trajectories of biogeochemical cycles, offer an opportunity to investigate power laws in ancient geological systems. In this study, I focus on the Phanerozoic sedimentary records of carbon, oxygen, sulfur, and strontium isotopes, which have well documented and extraordinarily comprehensive datasets. I perform statistical analyses on these datasets and show that the variations in the sedimentary records of the four isotopes exhibit power-law behaviors. The exponents of these power laws range between 2.2 and 2.9;this narrow interval indicates that the variations in carbon, oxygen, sulfur, and strontium isotopes likely belong to the same universality class, suggesting that these systematic power-law patterns are governed by universal, scale-free mechanisms. I then derive a general form for these power laws from a minimalistic model based on basic physical principles and geosystem-specific assumptions, which provides an interpretation for the power-law patterns from the perspective of thermodynamics. The fundamental mechanisms regulating such patterns might have been ubiquitous in paleoenvironments, implying that similar power-law behaviors may exist in the sedimentary records of other isotopes.
文摘Nd, Sr and O isotopic study on the spilite-keratophyre sequence in Xiqiu shows that its ∈_(Nd) values are inthe range of 4.02-5.26, and its ∈_(Sr) values, +1.4-2.6. According to the points of these data in the ∈_(Nd)-T,∈_(Sr)-T and ∈_(Nd)-∈_(Sr) diagrams, the spilite-keratophyre is interpreted as being slightly contaminated by crustalmaterials. Its δ^(18)O values are 3.9-5.0‰. The depletion of ^(18)O in the rocks resulted from the influence ofseawater hydrothermal alteration during or soon after the rock formation. Based on the isotopic characteristicsand available geochemical data, it is believed that the spilite-keratophyre was formed in the well-developedisland-arc environment during the Late Proterozoic subduction of the palaeo-Pacific plate beneath thesoutheastern margin of the Yangtze massif.
基金financially supported by the National Basic Research Program of China(973 Program,No. 2014CB440905)the Key Program of National Natural Science Foundation(No.41430315)the National Natural Science Foundation of China(Nos.41272111 and 41163001)
文摘The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD（H2O-SMOW） and δ18O（H2O-SMOW） values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ13C（PDB） values ranging from-6.2‰ to-4.1‰ and δ18O（SMOW） values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ34S（CDT） values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The 206Pb/204Pb,207Pb/204Pb and 208Pb/204Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.
文摘This paper focuses on the effect of the later hydrotherm on uraniferous leucogranites and the stages of uranium mineralization. Here, we review C-H-O stable isotope, elements and fluid geochemistry of uraniferous leucogranites in Gaudeanmus, Namibia. The results show that there is significant increasing amount of rare earth element from non-mineralized to uraniferous leucogra-nites, indicating the synchronization of REE enrichment and uranium mineralization. Uranium enrichment may have close relations with Pb, Th, Co, Ni, REE in this region, so REE and U evidently exist homology. There are at least two stages of uranium mineralization by later hydrothermal alteration: firstly, due to magnatic residual high temperature and low salinity fluid, the temperature of main metallogenetic epoch ranges from 470°C to 530°C, salinity ranges from 3.55% to 9.60% NaCleq, and C, H, O stable isotope is -23‰ - -13.6‰, -53.3‰ - -46.4‰, 7.71‰ - 8.81‰, respectively. Secondly, due to superim-posed hydrothermal fluid, the temperature, salinity, and C, H, O stable isotope is 150°C - 220°C, 4.65% - 19.05% NaCleq, -20.3‰ -?-3.7‰, -64.7‰ - -53.6‰, 1.49‰ - 1.99‰, respectively. The fluid for reformation is derived from postmagmatic fluid, mixed with a number of meteoric water.
基金financially supported by the China Geological Survey Program(Grant Nos.1212011121260,1212011220928)the National Natural Science Foundation of China(Project No.491755206)。
文摘The Gejiu-Bozushan-Laojunshan W-Sn polymetallic metallogenic belt(GBLB)in southeast Yunnan Province is an important part of the southwestern Yangtze Block in South China.Tin polymetallic mineralization in this belt includes the Niusipo,Malage,Songshujiao,Laochang and Kafang ore fields in the Gejiu area which are spatially and temporally associated with the Kafang-Laochang and Songshujiao granite plutons.These granites are characterized by variable A/CNK values(mostly>1.1,except for two samples with 1.09),high contents of SiO2(74.38-76.84 wt.%)and Al2 O3(12.46-14.05 wt.%)and variable CaO/Na2 O ratios(0.2-0.65)as well as high zirconδ18O values(7.74‰-9.86‰),indicative of S-type affinities.These rocks are depleted in Rb,Th,U,Ti,LREE[(La/Yb)N=1.4-20.51],Ba,Nb,Sr,and Ti and display strong negative Eu and Ba anomalies.The rocks possess high Rb/Sr and Rb/Ba ratios,relatively low initial 87Sr/86Sr ratios(0.6917-0.7101),and less radiogenicεNd(t)values(-8.0 to-9.1).The zircon grains from these rocks show negativeεHf(t)values in the range of-3.7 to-9.9 with mean TDM2(Nd)and TDM2(Hf)values of 1.57 Ga and 1.55 Ga.They show initial 207Pb/204Pb ranging from15.69 to 15.71 and 206Pb/204Pb from 18.36 to 18.70.Monazite from Songshujiao granites exhibits higher U and lower Th/U ratios,lowerδ18O values and higherεHf(t)values than those of the zircon grains in the KafangLaochang granites.The geochemical and isotopic features indicate that the Laochang-Kafang granites originated by partial melting of Mesoproterozoic crustal components including biotite-rich metapelite and metagraywacke,whereas the Songshujiao granites were derived from Mesoproterozoic muscovite-rich metapelite crustal source.Most zircon grains from the Songshujiao,Laochang and Kafang granites have high-U concentrations and their SIMS U-Pb ages show age scatter from 81.6 Ma to 88.6 Ma,80.7 Ma to 86.1 Ma and 82.3 Ma to 87.0 Ma,suggesting formation earlier than the monazite and cassiterite.Monazite SIMS U-Pb ages and Th-Pb ages of three same granite samples are consistent and show yielded 206 Pb/238U ages of 83.7±0.6 Ma,83.7±0.6 Ma,and 83.4±0.6 Ma,and 208Pb/232Th ages of 83.2±0.5 Ma,83.8±0.4 Ma,and 83.5±0.9 Ma,which are within the range of the SIMS zircon U-Pb ages from these rocks.The data constrain the crystallization of the granites at ca.83 Ma.In situ U-Pb dating of two cassiterite samples from the cassiterite-sulfide ore in the Songshujiao ore field and Kafang ore field,and two from the cassiterite-oxide+cassiterite bearing dolomite in the Laochang ore field yielded weighted mean 206 Pb/238U ages of 83.5±0.4 Ma(MSWD=0.6),83.5±0.4 Ma(MSWD=0.5),83.6±0.4 Ma(MSWD=0.6)and 83.2±0.7 Ma(MSWD=0.6),respectively.Combined with geological characteristics,the new geochronological data indicate that the formation of the granites and Sn polymetallic deposits are coeval.We correlate the magmatic and metallogenic event with lithospheric thinning and asthenosphere upwelling in continental extension setting in relation to the eastward subduction of the Neo-Tethys beneath the Sanjiang tectonic domain during Late Cretaceous.
文摘A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.
基金jointly by National Basic Research Program of China(973 Program) (2007CB411402)the Knowledge innovation project of Chinese Academy of Sciences(KZCX2-YW-Q04-05, KZCX2-YW-111-03)the National Natural Science Foundation of China(No.40573036).
文摘The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.
