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1.
An experimental study on the origin of ferric and ferrous carbonate-silicate melts, which can be considered as the potential metasomatic oxidizing agents and diamond forming media, was performed in the (Ca,Mg)CO3-SiO2-Al2O3-(Mg,Fe)(Cr,Fe,Ti)O3 system, at 6.3 GPa and 1350–1650 °C. At 1350–1450 °C and ?O2 of FMQ + 2 log units, carbonate–silicate melt, coexisting with Fe3 +-bearing ilmenite, pyrope-almandine and rutile, contained up to 13 wt.% of Fe2O3. An increase in the degree of partial melting was accompanied by decarbonation and melt enrichment with CO2, up to 21 wt.%. At 1550–1650 °C excess CO2 segregated as a separate fluid phase. The restricted solubility of CO2 in the melt indicated that investigated system did not achieve the second critical point at 6.3 GPa. At 1350–1450 °C and ?O2 close to CCO buffer, Fe2 +-bearing carbonate–silicate melt was formed in association with pyrope-almandine and Fe3 +-bearing rutile. It was experimentally shown that CO2-rich ferrous carbonate-silicate melt can be an effective waterless medium for the diamond crystallization. It provides relatively high diamond growth rates (3–5 μm/h) at P,T-conditions, corresponding to the formation of most natural diamonds.  相似文献   

2.
The Beaverlodge district in northern Saskatchewan is known for “vein-type” uranium mineralization. Most of the uranium deposits are spatially related to major structures, and hosted by ca. 3.2–1.9 Ga granitic rocks (and albitite derived from them) and by ca. 2.33 Ga Murmac Bay Group amphibolite, all of which are unconformably overlain locally by deformed but unmetamorphosed redbeds of the ca. 1.82 Ga Martin Group, and by the flat-lying ca. 1.75–1.5 Ga Athabasca Group. The uranium mineralization is mainly hosted in fault rocks (breccias) and carbonate ± quartz ± albite veins, referred to as breccia-style and vein-style mineralization, respectively, with the latter being the focus of this study. Most of the mineralized veins occur in the basement rocks, although some crosscut the Martin Group. This study examines the field, petrographic, fluid inclusion and C-O isotope characteristics of mineralized and non-mineralized veins from 19 deposits/occurrences as well as from the Martin Group, with an aim to better understand the mineralizing environment and processes.The coexistence of liquid-dominated (L + V), vapour-dominated (V + L) and vapour-only (V) fluid inclusions within individual fluid inclusion assemblages (FIAs) in the veins suggests fluid immiscibility and heterogeneous trapping. The L + V inclusions with the lowest homogenization temperatures (Th) within individual FIAs are interpreted to represent homogeneous trapping of the liquid phase, which yield Th values from 78° to 330 °C (mainly 100° to 250 °C), and salinities from 0.2 to 30.8 wt.% NaCl equivalent. Mass spectrometric analysis of bulk fluid inclusions shows that the volatiles are dominated by H2O (average 97.2 mol%), with minor amounts of CO2, CH4, H2, O2, N2, Ar and He. Fluid pressures were estimated to be < 200 bars based on the inference of fluid immiscibility, fluid temperatures of 100° to 250 °C, and low concentrations of non-aqueous volatiles (< 3 mol%). The δ18OVPDB and δ13CVPDB of carbonate minerals associated with mineralization range from − 20.5 to − 8.9‰ and − 10.1 to − 0.9‰, respectively. The δ18OVSMOW values of the parent fluids calculated using the Th values range from − 9.6 to + 17.0‰, with the majority from 0 to + 5.0‰. O isotopes of paired equilibrium quartz and calcite, analyzed by secondary ion mass spectrometry (SIMS), yield temperatures from 161° to 248 °C, which are consistent with the fluid inclusion data.The new fluid inclusion and stable isotope data are inconsistent with a metamorphic or magmatic-hydrothermal model as proposed in some previous studies (for breccia-style and vein-style mineralization), but rather support a model in which the vein-type uranium mineralization took place at relatively low temperature (100° to 250 °C) and shallow (< 2 km) conditions, with fluid pressure fluctuating between hydrostatic and sub-hydrostatic regimes, possibly related to episodic faulting. The mineralizing fluids were mainly sourced from the Martin Lake Basin, and uraninite was precipitated as a result of mixing between this basin-derived fluid and fluids carrying reducing agents (Fe2 +, CH4) derived from the basement, although fluid-rock reactions and fluid immiscibility may have also played a role.  相似文献   

3.
In this paper I present results of IR spectroscopic measurements of water solubility in Al-bearing periclase and ferropericlase (Mg# = 88) synthesized at 25 GPa and 1400–2000 °C. The IR spectra of their crystals show narrow absorption peaks at 3299, 3308, and 3474 cm?1. The calculated H2O contents are 11–25 ppm in periclase (Al2O3 = 0.9–1.2 wt.%) and 14–79 ppm in ferropericlase (Al2O3 = 0.9–2.9 wt.%). Ferropericlase contains more H2O and Al2O3 than periclase at 1800–2000 °C. I suggest that addition of Al2O3 does not influence the solubility of water in ferropericlase but can favor the additional incorporation of Fe2O3 into the structure. The incorporation of Fe3+ into ferropericlase increases water solubility as a result of iron reduction to Fe2+. It is shown that water has limited solubility in ferropericlase from mantle peridotite; therefore, ferropericlase cannot be considered an important hydrogen-bearing mineral in the lower mantle.  相似文献   

4.
Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe2O3)? : (FeO/Fe2O3)??, where (FeO/Fe2O3)? and (FeO/Fe2O3)?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe2O3 ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr2O3) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr2O3), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N2, with an error of σ = 0.19 (N = T · 10?2, T is temperature in °C).  相似文献   

5.
The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO2 inclusions, CO2–H2O inclusions, hydrocarbon inclusions, and hydrocarbon–H2O inclusions. The ore-forming fluids are characterized by a H2O + CO2 + CH4 ± N2 system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H2O + NaCl → H2O + NaCl + CO2 + CH4 ± N2 → H2O + NaCl ± CH4 ± CO2 with a slight decrease in homogenization temperature and salinity. The δ18O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δDH2O and calculated δ18OH2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ13CPDB and δ18OSMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H2O–NaCl–CO2 fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.  相似文献   

6.
Orogenic gold mineralization in the Amalia greenstone belt is hosted by oxide facies banded iron-formation (BIF). Hydrothermal alteration of the BIF layers is characterized by chloritization, carbonatization, hematization and pyritization, and quartz-carbonate veins that cut across the layers. The alteration mineral assemblages consist of ankerite-ferroan dolomite minerals, siderite, chlorite, hematite, pyrite and subordinate amounts of arsenopyrite and chalcopyrite. Information on the physico-chemical properties of the ore-forming fluids and ambient conditions that promoted gold mineralization at Amalia were deduced from sulfur, oxygen and carbon isotopic ratios, and fluid inclusions from quartz-carbonate samples associated with the gold mineralization.Microthermometric and laser Raman analyses indicated that the ore-forming fluid was composed of low salinity H2O-CO2 composition (~3 wt% NaCl equiv.). The combination of microthermometric data and arsenopyrite-pyrite geothermometry suggest that quartz-carbonate vein formation, gold mineralization and associated alteration of the proximal BIF wall rock occurred at temperature-pressure conditions of 300 ± 30 °C and ∼2 kbar. Thermodynamic calculations at 300 °C suggest an increase in fO2 (10−32–10−30 bars) and corresponding decrease in total sulfur concentration (0.002–0.001 m) that overlapped the pyrite-hematite-magnetite boundary during gold mineralization. Although hematite in the alteration assemblage indicate oxidizing conditions at the deposit site, the calculated low fO2 values are consistent with previously determined high Fe/Fe + Mg ratios (>0.7) in associated chlorite, absence of sulfates and restricted positive δ34S values in associated pyrite. Based on the fluid composition, metal association and physico-chemical conditions reported in the current study, it is confirmed that gold in the Amalia fluid was transported as reduced bisulfide complexes (e.g., Au(HS)2−). At Amalia, gold deposition was most likely a combined effect of increase in fO2 corresponding to the magnetite-hematite buffer, and reduction in total sulfur contents due to sulfide precipitation during progressive fluid-rock interaction.The epigenetic features coupled with the isotopic compositions of the ore-forming fluid (δ34SΣS = +1.8 to +2.3‰, δ18OH2O = +6.6 to +7.9‰, and δ13CΣC = −6.0 to −7.7‰ at 300–330 °C) are consistent with an externally deep-sourced fluid of igneous signature or/and prograde metamorphism of mantle-derived rocks.  相似文献   

7.
Chromite mineralization in metamorphosed dunites from the southern Klyuchevskoy dunite-harzburgite ultramafic complex (Central Urals) has been investigated using geomagnetic surveys along with laboratory studies of ore-forming and accessory spinels of the same genetic type. Magnetization in the study area is carried mainly by accessory Fe-Cr-spinel of a variable Fe2 +(Cr2 -xFex3 +)O4 composition. Metamorphism caused changes in element contents and in both crystal and magnetic structure of the primary nonmagnetic accessory spinel, unlike the almost fresh ore-forming spinel. Thus, ore bodies stand against their host rocks, which is a prerequisite for the use of geomagnetic surveys for exploration of podiform chromite deposits in dunite-harzburgite complexes. Ground magnetic surveys at a test site composed of faulted rocks bearing disseminated chromite mineralization in metamorphosed dunites resolved a chromite ore zone and a fault block boundary showing up as geomagnetic anomalies. Laboratory studies using high technologies (thermomagnetic analysis at 4 to 1000 K, as well as magnetic resonance and magnetic force spectroscopy) revealed, for the first time, magnetic clusters (superparamagnetic phases) in primary nonmagnetic accessory spinel, which are responsible for the magnetic properties of the host rocks. Microscale variations in Cr-spinel correlate with the geomagnetic anomalies recorded by field surveys at the test site.© 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.  相似文献   

8.
The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H2O–CO2 system fluid, coexisting with NaCl–H2O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H2O–CO2 system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ18OH2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ13CPDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO32 − or CO2 in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with 206Pb/204Pb ranging from 17.958 to 18.587, 207Pb/204Pb ranging from 15.549 to 15.701, and 208Pb/204Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.  相似文献   

9.
The Shangdan suture zone (SSZ) is the main collisional boundary between the North China Craton and the South China Craton, along which discontinuous Paleozoic ophiolites and subduction–accretion related volcanic arc assemblages occur. Here we report the petrology, geochemistry, geochronology and phase equilibria modeling of garnet amphibolite from the Songshugou ophiolite which is one of the largest ophiolite outcrops in the northern side of the SSZ. From petrological studies, we identify: (1) prograde stage, defined by garnet + clinopyroxene + calcic amphibole + ilmenite + rutile + epidote + plagioclase + quartz; (2) peak stage with garnet + clinopyroxene + ilmenite + rutile + quartz; and (3) retrograde stage with amphibole + plagioclase + titanite + ilmenite. Our pseudosection analysis defines stability of the peak assemblage at 750–850 °C, 15–19 kbar and traces a clockwise P–T path in the system Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (NCFMASHTO), suggesting high pressure (HP) metamorphism. Subsequently, the rocks experienced rapid decompression and cooling. LA-ICP-MS U-Pb analyses of zircons from the garnet amphibolite yield a weighted mean 206Pb/238U age of 515 ± 12 Ma. This Early Paleozoic metamorphic age represents the emplacement time of the Songshugou ophiolite, and suggests that the HP metamorphism is possibly related to the northward deep subduction of the Shangdan oceanic crust in Early Paleozoic.  相似文献   

10.
《Chemical Geology》2006,225(1-2):40-60
Fluorite is the most common fluoride mineral in magmatic silicic systems and its crystallization can moderate or buffer fluorine concentrations in these settings. We have experimentally determined fluorite solubility and speciation mechanisms in haplogranitic melts at 800–950 °C, 100 MPa and aqueous-fluid saturation. The starting haplogranite compositions: peraluminous (alumina saturation index, ASI = 1.2), subaluminous (ASI = 1.0) and peralkaline (ASI = 0.8) were variably doped with CaO or F2O−1 in the form of stoichiometric mineral or glass mixtures. The solubility of fluorite along the fluorite–hydrous haplogranite binaries is low: 1.054 ± 0.085 wt.% CaF2 (peralkaline), 0.822 ± 0.076 wt.% (subaluminous) and 1.92 ± 0.15 wt.% (peraluminous) at 800 °C, 100 MPa and 10 wt.% H2O, and exhibits a minimum at ASI ∼ 1. Fluorite saturation isotherms are strongly hyperbolic in the CaO–F2O−1 space, suggesting that fluorite saturation is controlled by the activity product of CaO and F2O−1, i.e., these components are partially decoupled in the melt structure. The form of fluorite liquidus isotherms implies distinct roles of fluorite crystallization: in Ca-dominant systems, fluorite crystallization is controlled by the fluorine concentration in the melt only and remains nearly independent of calcium contents; in F-rich systems, the crystallization of fluorite is determined by CaO contents and it does not buffer fluorine concentration in the melt. The apparent equilibrium constant, K, for the equilibrium CaO + cF2O−1 = CaF2 (+ associates) is log K= − (2.449 ± 0.085)·Al2O3exc + (4.902 ± 0.066); the reaction-stoichiometry parameter varies as follows: c= − (0.92 ± 0.11)·Al2O3exc + (1.042 ± 0.084) at 800 °C, 100 MPa and fluid saturation where Al2O3exc are molar percent alumina in excess over alkali oxides. The reaction stoichiometry, c, changes at subaluminous composition: in peralkaline melts, competition of other network modifiers for excess fluorine anions leads to the preferential alkali–F short-range order, whereas in peraluminous compositions, excess alumina associates with calcium cations to form calcioaluminate tetrahedra. The temperature dependence of fluorite solubility is described by the binary symmetric Margules parameter, W = 36.0 ± 1.4 kJ (peralkaline), 39.7 ± 0.5 kJ (subaluminous) and 32.8 ± 0.7 kJ (peraluminous). The strong positive deviations from ideal mixing imply the occurrence of CaF2–granite liquid–liquid immiscibility at temperatures above 1258 °C, which is consistent with previous experimental data. These experimental results suggest very low solubilities of fluorite in Ca-rich melts, consistent with the lack of fluorine enrichment in peralkaline rhyolites and calc-alkaline batholiths. On the other hand, high CaO concentrations necessary to crystallize fluorite in F-rich peraluminous melts are not observed in nature and thus magmatic crystallization of fluorite in topaz-bearing silicic suites is suppressed. A procedure for calculating fluorite solubility and the liquidus isotherms for a whole-rock composition and temperature of interest is provided.  相似文献   

11.
The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ13CPDB (−7.0‰ to −5.0‰) and δ18OSMOW (7.2‰ to 12.7‰) than Calcite II (δ13CPDB = −4.5‰ to −2.3‰; δ18OSMOW = 10.7‰ to 19.4‰). In the δ13CPDB vs. δ18OSMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ13CPDB = −4.8‰ to −0.3‰; δ18OSMOW = 10.2‰ to 23.9‰) also shows a positive δ13CPDB vs. δ18OSMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO2 degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.  相似文献   

12.
To understand Holocene climate evolutions in low-latitude region of the western Pacific, paired δ18O and Mg/Ca records of planktonic foraminifer Globigerinoides ruber (250–300 μm, sensu stricto, s.s.) from a marine core ORI715-21 (121.5°E, 22.7°N, water depth 760 m) underneath the Kuroshio Current (KC) off eastern Taiwan were analyzed. Over the past 7500 years, the geochemical proxy-inferred sea surface temperature (SST) hovered around 27–28 °C and seawater δ18O (δ18OW) slowly decreased 0.2–0.4‰ for two KC sites at 22.7° and 25.3°N. Comparison with a published high-SST and high-salinity equatorial tropical Pacific record, MD98-2181 located at the Mindanao Current (MC) at 6.3°N, reveals an anomalous time interval at 3.5–1.5 kyr ago (before 1950 AD). SST gradient between the MC site and two KC site decrease from 1.5–2.0 °C to only 0–1 °C, and δ18OW from 0.1–0.3‰ to 0‰ for this 2-kyr time window. The high SST and low gradient could result from a northward shift of the North Equatorial Current, which implies a weakened KC. The long-term descending δ18OW and increasing precipitation in the entire low-latitude western Pacific and the gradually decreasing East Asian summer monsoonal rainfall during middle-to-late Holocene is likely caused by different land and ocean responses to solar insolation and/or enhanced moisture transportation from the Atlantic to Pacific associated with the southward movement of ITCZ.  相似文献   

13.
Pure-iron end-member hibbingite, Fe2(OH)3Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe2(OH)3Cl(s), the pure-iron end-member of hibbingite (FeII, Mg)2(OH)3Cl(s), and Fe(OH)2(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe2(OH)3Cl(s) + 3H+ ? 3 H2O + 2 Fe2+ + Cl?,the solubility constant of Fe2(OH)3Cl(s) at infinite dilution and 25 °C has been found to be log10 K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)2(s) + 2H+ ? 2 H2O + Fe2+,the solubility constant of Fe(OH)2 at infinite dilution and 25 °C has been found to be log10 K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe2(OH)3Cl(s) and Fe(OH)2(s), the Na+–Fe2+ pair Pitzer interaction parameter θNa+/Fe2+ has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)2(s) to Fe2(OH)3Cl(s). Additionally, when Fe2(OH)3Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.  相似文献   

14.
The large (>180 Kt WO3 and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH4-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO2-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ18OH2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ34S = −6.9 to −6.2‰) and carbon (δ13Cfluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ18O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ34S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ13Cfluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ13Cfluid = −16.4 to −14.5‰) and late (δ13Cfluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO2 removal due to boiling of CO2-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.  相似文献   

15.
The effect of fluorine on the solubilities of Mn-columbite (MnNb2O6), Mn-tantalite (MnTa2O6), zircon (ZrSiO4) and hafnon (HfSiO4) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab72Or28) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P2O5, 1.05 wt.% Li2O and 1.83 wt.% B2O3. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF3 to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb2O5] and [MnO] 1 [Ta2O5] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10− 4 (mol2/kg2), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10− 4 (mol/kg) ZrO2 and 4.04 ± 0.2 × 10− 4 (mol/kg) HfO2 for melts with 0 wt.% F to 3.81 ± 0.3 × 10− 4 (mol/kg) ZrO2 and 6.18 ± 0.04 × 10− 4 (mol/kg) HfO2 for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.  相似文献   

16.
Relative to the North China Craton, the subcontinental lithospheric mantle (SCLM) beneath the Central Asian Orogenic Belt is little known. Mantle-derived peridotite xenoliths from the Cenozoic basalts in the Xilinhot region, Inner Mongolia, provide samples of the lithospheric mantle beneath the eastern part of the belt. The xenoliths are predominantly lherzolites with minor harzburgites, and can be subdivided into three groups, based on the REE patterns of clinopyroxenes. Group 1 peridotites (LREE-enriched), with low modal Cpx (3–7%), high Mg# in olivine (> 90.6) and Cr# in spinel (> 43.8), low whole-rock CaO + Al2O3 contents (1.62–3.22 wt.%) and estimated temperatures of 1043–1126 °C, represent moderately refractory SCLM that has experienced carbonatite-related metasomatism. Group 2 peridotites (LREE-depleted), with high modal Cpx (9–13%), low Mg# in olivine (< 90.6) and Cr# in spinel (< 20.0), high whole-rock CaO + Al2O3 contents (4.93–6.37 wt.%) and estimated temperatures of 814–970 °C, show affinity with Phanerozoic fertile SCLM that has undergone silicate-related metasomatism. Group 3 peridotites (convex-upward REE patterns), show wide ranges of olivine-Mg# (88.4–90.6), spinel-Cr# (11.5–47.6), and modal Cpx (3–14%) that overlap Groups 1 and 2. Their spinels have high TiO2 contents (> 0.41 wt.%), implying involvement of reactions between melt and peridotites. The estimated temperatures of Group 3 (1033–1156 °C) are similar to those of Group 1. We suggest that the pre-existing moderately refractory lithospheric mantle (i.e., Group 1) beneath the eastern part of the Central Asian Orogenic Belt was strongly penetrated by upwelling asthenospheric material, and the cooling of this material produced fertile lithospheric mantle (i.e., Group 2). The present lithospheric mantle of this area consists of interspersed volumes of younger fertile and older more refractory lithosphere, with the fertile type dominating the shallower levels of the mantle.  相似文献   

17.
Changes in the orbital parameters, solar output, and ocean circulation are widely considered as main drivers of the Holocene climate. Yet, the interaction between these forcings and the role that they play to produce the pattern of changes observed in different domains of the climate system remain debated. Here, we present new early to middle Holocene season-specific sea surface temperature (SST) and δ18Oseawater results, based on organic-walled dinoflagellate cyst and planktonic foraminiferal data from two sediment cores located in the central (SL21) and south-eastern (LC21) Aegean Sea (eastern Mediterranean). Today, this region is affected by high to mid latitude climate in winter and tropical/subtropical climate in summer. The reconstructed δ18Oseawater from LC21 displays a marked (～1.3%) negative shift between 10.7 and 9.7 ka BP, which represents the regional expression of the orbitally driven African monsoon intensification and attendant freshwater flooding into the eastern Mediterranean. A virtually contemporaneous shift, of the same sign and magnitude, is apparent in the δ18Ospeleothem record from Soreq Cave (Northern Israel), an important part of which may therefore reflect a change in the isotopic composition of the moisture source region (Aegean and Levantine Seas). Our SST reconstructions show that Aegean winter SSTs decreased in concert with intensifications of the Siberian High, as reflected in the GISP2 nss [K+] record. Specifically, three distinct sea surface cooling events at 10.5, 9.5–9.03 and 8.8–7.8 ka BP in the central Aegean Sea match increases in GISP2 nss [K+]. These events also coincide with dry interludes in Indian monsoon, hinting at large (hemispheric) scale teleconnections during the early Holocene on centennial timescales. A prominent short-lived (～150 years) cooling event in core SL21 – centred on 8.2 ka BP – is coeval to the ‘8.2 ka BP event’ in the Greenland δ18Oice, which is commonly linked to a melt-water related perturbation of the Atlantic Meridional Overturning Circulation and associated ocean heat transport. By deciphering the phasing between a recently published record of reduced overflow from the Nordic Seas into the northern North Atlantic, the Greenland δ18Oice ‘8.2 ka BP event’ anomaly, and the short-lived cooling in SL21, we demonstrate severe far-field impacts of this North Atlantic event in the Aegean Sea. The Aegean is isolated from the North Atlantic oceanic circulation, so that signal transmission must have been of an atmospheric nature.  相似文献   

18.
The Wenjiaping and Wulaxi granite plutons are located in the Jianglang dome, which is a key domain for providing deep insight into the tectonic evolution of the Songpan-Ganzi Orogen. Two granites are composed chiefly of K-feldspar, quartz, biotite with minor plagioclase and hornblende. This study presents zircon U-Pb chronology, geochemistry and Hf isotope data to explore their petrogenesis and metallogenic implications. Zircon U-Pb dating provides crystallization ages of 164.5 ± 0.9 Ma and 163.4 ± 0.9 Ma for the Wenjiaping granite, and 164.3 ± 1.7 Ma for the Wulaxi granite. This indicates that they were formed synchronously. They also contain inherited zircons related to the Rodinia and Gondwana supercontinents and the Emeishan large igneous province. Their mineral assemblages lack peraluminous (e.g., garnet and cordierite) and high-temperature (e.g., pyroxene and fayalite) minerals. They are characterized by low A/CNK (1.10–0.99), FeOT/MgO (8.55–2.83) and K2O/N2O ratios (1.34–0.51) with low Zr + Nb + Ce + Y concentrations (average 258 ppm) and zircon saturation temperatures (781–651 °C). Their Al2O3, P2O5 and SiO2 contents show negative correlations, and they thus fit the I-type granite definition. Some major and trace elements exhibit strong correlations, implying extensive fractional crystallization (e.g., hornblende and ilmenite) during the magma evolution. Two granites show enrichment in light rare earth elements and large ion lithophile elements, and depletion in high field strength elements. They have low Mg# values (38.7–17.3) and Y/Nb ratios (0.45–0.16), and yield dominantly negative εHf(t) values (1.4–−13.9), indicating a heterogeneous source and their derivation from remelting of ancient continental crust (e.g., Mesoproterozoic Liwu Group in this region) with minor juvenile crust. Combined with prior studies, we conclude that the Wenjiaping and Wulaxi granites were formed in a post-collisional extensional regime, and were responsible for the 163.7–151.1 Ma magmatic hydrothermal Cu-W mineralization in the Jianglang dome. In addition, two granite plutons intrude this dome and they are undeformed, implying that the doming was during the Early to Middle Jurassic.  相似文献   

19.
The Jílové deposit in the central part of the Bohemian Massif represents a vein to stockwork type of orogenic-type gold deposit. It is hosted by Neoproterozoic rocks of the Jílové Belt and by various magmatic dikes related to the ~ 355 to ~ 335 Ma Central Bohemian Plutonic Complex. The deposit is situated along the terrane boundary of the Teplá Barrandian and Moldanubian units.The deposit offered an exceptional opportunity to trace O, C, S and Sr stable isotope evolution of parent fluids based on combined mineralogical and geochemical study of carbonate, quartz, scheelite, and sulfide minerals, which represent six stages of mineralization, including the gold-bearing event.Stable isotope data and mineral and isotope thermometry indicate gangue and ore mineral formation between ~ 350 °C and < 100 °C, which can be divided into 6 stages. Scheelite-bearing assemblages (stages 2–3) precipitated at 292 ± 8 °C from a fluid with calculated values: δ18OSMOW = + 4.2 ± 0.5‰ and δ13CPDB = − 11 ± 1‰. Gold precipitation (stage 5) probably started at about 300 °C, but the major event probably occurred at 230 ± 30 °C from a fluid with more variable isotope values (δ18OSMOW = + 2.5 to + 5‰ and δ13CPDB = − 9 to − 13.5‰). The carbon speciation was characterized by predomination of dissolved CO2 (H2CO3ap.) in the fluids. Some gold, however, undoubtedly precipitated from bicarbonate dominated fluids even at < 120 °C.Extreme variations in the δ18O values of carbonate minerals, obtained from sampling profiles across individual veins with macroscopic gold, revealed severe thermal gradients during vein formation (~ 50 to ~ 100 °C difference of crystallization temperatures between the vein margin and core).The sulfur stable isotope composition of sulfide minerals indicates the dominant role of sulfur remobilization from Neoproterozoic rocks and stratiform mineralizations of the Jílové Belt by Variscan hydrothermal fluids. Similarly, the Sr-isotope composition of carbonates indicates both relatively primitive (87Sr/86Sr = 0.7055) and more evolved (87Sr/86Sr ~ 0.7090) fluid compositions, probably indicating fluid exchange with the Jílové Belt and the Central Bohemian Plutonic Complex rocks, respectively.Age determination of hydrothermal muscovite (related to stage 2) via 40Ar/39Ar indicated an age of 339.0 ± 1.5 Ma for the quartz veins. The mineralization is essentially coeval with the late intrusive phases of the Central Bohemian Plutonic Complex (i.e. the ultrapotassic suite) and with late-orogenic large-scale tectonic movements at the boundary between the two crustal terranes (Teplá-Barrandian and Moldanubian).Based on evaluation of the available age data on the hydrothermal and magmatic activity within the broader area of the Central Bohemian Plutonic Complex, we suggest two intervals of gold mineralization: 347 to 341 Ma and 340 to 337 Ma. The former interval overlaps with the intrusive activity of the Blatná high-K suite (granodiorite). The associated gold deposits (Mokrsko and Petráčkova hora) exhibit strong affiliation to the intrusion-related-gold-type deposit. The later interval overlaps with the ultrapotassic magmatism and is associated with more or less “classical” orogenic-gold-type deposits (Jílové, Bělčice, Libčice deposits).  相似文献   

20.
The Dongping gold deposit hosted in syenites is one of the largest hydrothermal gold deposits in China and composed of ore veins in the upper parts and altered zones in the lower parts of the ore bodies. Pervasive potassic alteration and silicification overprint the wall rocks of the ore deposit. The alteration minerals include orthoclase, microcline, perthite, quartz, sericite, epidote, calcite, hematite and pyrite, with the quartz, pyrite and hematite assemblages closely associated with gold mineralization. The phases of hydrothermal alteration include: (i) potassic alteration, (ii) potassic alteration - silicification, (iii) silicification - epidotization - hematitization, (iv) silicification - sericitization - pyritization and (v) carbonation. Mass-balance calculations in potassic altered and silicified rocks reveal the gain of K2O, Na2O, SiO2, HFSEs and transition elements (TEs) and the loss of REEs. Most major elements were affected by intense mineral reactions, and the REE patterns of the ore are consistent with those of the syenites. Gold, silver and tellurium show positive correlation and close association with silicification. Fluid inclusion homogenization temperatures in quartz veins range from 154 °C to 382 °C (peak at 275 °C–325 °C), with salinities of 4–9 wt.% NaCl equiv. At temperatures of 325 °C the fluid is estimated to have pH = 3.70–5.86, log fO2 = − 32.4 to − 28.1, with Au and Te transported as Au (HS)2− and Te22 − complexes. The ore forming fluids evolved from high pH and fO2 at moderate temperatures into moderate-low pH, low fO2 and low temperature conditions. The fineness of the precipitated native gold and the contents of the oxide minerals (e.g., magnetite and hematite) decreased, followed by precipitation of Au- and Ag-bearing tellurides. The hydrothermal system was derived from an alkaline magma and the deposit is defined as an alkaline rock-hosted hydrothermal gold deposit.  相似文献   

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