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1.
Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced 56Fe/54Fe ratios for Fe(II)aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO3) and ca. +0.9‰ for Ca-substituted siderite (Ca0.15Fe0.85CO3) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have 56Fe/54Fe ratios that are up to 1‰ lower than Fe(II)aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)aq.The relative order of δ56Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ56Fe >0‰, the calculated δ56Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ56Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ56Fe values. Based on this experimental study, formation of low-δ56Fe Fe(II)aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.  相似文献   

2.
The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ18O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ18O–δ56Fe variations in magnetite is a strong increase in δ18OMt and a mild decrease in δ56Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

3.
Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in 56Fe/54Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ56Feclinopyroxene-olivine fractionation and the δ56Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ56Feclinopyroxene-garnet fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ56Feclinopyroxene-garnet fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.  相似文献   

4.
We present the iron isotope composition of primary, diagenetic and metamorphic minerals in five samples from the contact metamorphosed Biwabik Iron Formation. These samples attained peak metamorphic temperatures of <200, <340, ∼500, <550, and <740°C respectively. δ56Fe of bulk layers ranges from −0.8 to +0.8‰; in some samples the layers may differ by >1‰ on the millimeter scale. Minerals in the lowest grade samples consistently show a sequence in which δ56Fe of magnetite > silicate ≥ carbonate. The inter-mineral Fe isotope differences vary in a fashion that cannot be reconciled with theoretical temperature-dependent fractionation factors. Textural evidence reveals that most, if not all, magnetite in the Biwabik Formation is diagenetic, not primary, and that there was tremendous element mobility during diagenesis. The short duration of contact metamorphism allowed diagenetic magnetite compositions to be preserved throughout prograde metamorphism until at least the appearance of olivine. Magnetite compositions therefore act as an isotope record of the environment in which these sediments formed. Larger-scale fluid flow and longer timescales may allow equilibration of Fe isotopes in regionally metamorphosed rocks to lower temperatures than in contact metamorphic environments, but weakly regionally metamorphosed rocks may preserve small-scale Fe isotopic heterogeneities like those observed in the Biwabik Iron Formation. Importantly, Fe isotope compositions that are characteristic of chemical sedimentation or hydrothermal processes are preserved at low grade in the form of large inter-mineral variations, and at high grade in the form of unique bulk rock compositions. This observation confirms earlier work that has suggested that Fe isotopes can be used to identify sedimentary processes in the Precambrian rock record. An erratum to this article can be found at  相似文献   

5.
 Hydrogen and oxygen isotope analyses have been made of hydrous minerals in gabbros and basaltic xenoliths from the Eocene Kap Edvard Holm intrusive complex of East Greenland. The analyzed samples are of three types: (1) primary igneous hornblendes and phlogopites that crystallized from partial melts of hydrothermally altered basaltic xenoliths, (2) primary igneous hornblendes that formed during late–magmatic recrystallization of layered gabbroic cumulates, and (3) secondary actinolite, epidote and chlorite that formed during subsolidus alteration of both xenoliths and gabbros. Secondary actinolite has a δ18O value of −5.8‰ and a δD value of −158‰. These low values reflect subsolidus alteration by low–δ18O, low–δD hydrothermal fluids of meteoric origin. The δD value is lower than the −146 to −112‰ values previously reported for amphiboles from other early Tertiary meteoric–hydrothermal systems in East Greenland and Scotland, indicating that the meteoric waters at Kap Edvard Holm were isotopically lighter than typical early Tertiary meteoric waters in the North Atlantic region. This probably reflects local climatic variations caused by formation of a major topographic dome at about the time of plutonism and hydrothermal activity. The calculated isotopic composition of the meteoric water is δD=−110 ± 10‰, δ18O ≈−15‰. Igneous hornblendes and phlogopites from pegmatitic pods in hornfelsed basaltic xenoliths have δ18O values between −6.0 and −3.8‰ and δD values between −155 and −140‰. These are both much lower than typical values of fresh basalts. The oxygen isotope fractionations between pegmatitic hornblendes and surrounding hornfelsic minerals are close to equilibrium fractionations for magmatic temperatures, indicating that the pegmatites crystallized from low–δ18O partial melts of xenoliths that had been hydrothermally altered and depleted in 18O prior to stoping. The pegmatitic minerals may have crystallized with low primary δD values inherited from the altered country rocks, but these values were probably overprinted extensively by subsolidus isotopic exchange with low–δD meteoric–hydrothermal fluids. This exchange was facilitated by rapid self–diffusion of hydrogen through the crystal structures. Primary igneous hornblendes from the plutonic rocks have δ18O values between +2.0 and +3.2‰ and δD values between −166 and −146‰. The 18O fractionations between hornblendes and coexisting augites are close to equilibrium fractionations for magmatic temperatures, indicating that the hornblendes crystallized directly from the magma and subsequently underwent little or no oxygen exchange. The hornblendes may have crystallized with low primary δD values, due to contamination of the magma with altered xenolithic material, but the final δD values were probably controlled largely by subsolidus isotopic exchange. This inference is based partly on the observation that coexisting plagioclase has been extensively depleted in 18O via a mineral–fluid exchange reaction that is much slower than the hydrogen exchange reaction in hornblende. It is concluded that all hydrous minerals in the study area, whether igneous or secondary, have δD values that reflect extensive subsolidus isotopic equilibration with meteoric–hydrothermal fluids. Received: 22 March 1994 / Accepted: 26 January 1995  相似文献   

6.
Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ18O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ18O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by 18O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δglaucophane−garnet = 1.37 ± 0.24‰ and Δomphacite−garnet = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 106/T 2 (in Kelvin) of Aglaucophane−garnet = 0.87 ± 0.15 and Aomphacite−garnet = 0.72 ± 0.24. A fractionation of Δglaucophane–actinolite = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999  相似文献   

7.
The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ56Fe values for magnetite record a strong inheritance from Fe3+ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe3+ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ56Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ56Fe values and was produced by DIR. Most siderite has slightly negative δ56Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ56Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ56Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.  相似文献   

8.
Measurable molybdenum isotope fractionation in molybdenites from different ore deposits through time provides insights into ore genesis and a new technique to identify open-system behavior of Re–Os in molybdenites. Molybdenite samples from six porphyry copper deposits, one epithermal polymetallic vein deposit, four skarns, and three Fe-oxide Cu–Au deposits were analyzed. The δ97Mo‰ (where ) for all samples varied from 1.34 ± 0.09‰ to −0.26 ± 0.04‰. This is the largest molybdenum isotopic variation in molybdenite from high-temperature ore deposits recorded to date. δ97Mo‰ of molybdenite varies as a function of the deposit type and the rhenium and osmium concentrations of the samples. Isotope values for Mo also vary within the individual deposits. In general, molybdenites from porphyry copper deposits have the lightest values averaging 0.07 ± 0.23‰ (1σ). Molybdenites from the other deposit types average 0.49 ± 0.26‰ (1σ). The variations could be related to the fractionation of Mo into different mineral phases during the ore-forming processes. A comparison of the Mo isotope ratios and the Re–Os ages obtained from the same aliquot may possess a geochronological evaluation tool. Samples that yielded robust ages have different Mo isotopic compositions in comparison to samples that yielded geologically unreasonable ages. Another observed relationship between the Re–Os and Mo isotope data reveals a weak correspondence between Re concentration and Mo isotope composition. Molybdenites with higher concentrations of Re correspond to lighter Mo isotope values.  相似文献   

9.
 Dreissena polymorpha is an exotic freshwater bivalve species which was introduced into the Great Lakes system in the fall of 1985 through the release of ballast water from European freighters. Utilizing individual growth rings of the shells, the stable isotope distribution (δ18O and δ13C) was determined for the life history of selected samples which were collected from the western basin of Lake Erie. These bivalves deposit their shell in near equilibrium with the ambient water and thus reflect any annual variation of the system in the isotopic records held within their shells. Observed values for δ18O range from -6.64 to –9.46‰ with an average value of –7.69‰ PDB, while carbon values ranged from –0.80 to –4.67‰ with an average value of –1.76‰ PDB. Dreissena polymorpha shells incorporate metals into their shells during growth. Individual shell growth increments were analyzed for Pb, Fe, Mg, Mn, Cd, Cu, and V concentrations. The shells show increased uptake of certain metals during periods of isotopic enrichment which correspond with warmer water temperatures. Since metals are incorporated into the shells, the organism may be useful as a biomonitor of metal pollution within aquatic environments. Received: 31 October 1996 · Accepted: 21 May 1997  相似文献   

10.
We present high-precision iron and magnesium isotopic data for diverse mantle pyroxenite xenoliths collected from Hannuoba, North China Craton and provide the first combined iron and magnesium isotopic study of such rocks. Compositionally, these xenoliths range from Cr-diopside pyroxenites and Al-augite pyroxenites to garnet-bearing pyroxenites and are taken as physical evidence for different episodes of melt injection. Our results show that both Cr-diopside pyroxenites and Al-augite pyroxenites of cumulate origin display narrow ranges in iron and magnesium isotopic compositions (δ57Fe = ?0.01 to 0.09 with an average of 0.03 ± 0.08 (2SD, n = 6); δ26Mg = ? 0.28 to ?0.25 with an average of ?0.26 ± 0.03 (2SD, n = 3), respectively). These values are identical to those in the normal upper mantle and show equilibrium inter-mineral iron and magnesium isotope fractionation between coexisting mantle minerals. In contrast, the garnet-bearing pyroxenites, which are products of reactions between peridotites and silicate melts from an ancient subducted oceanic slab, exhibit larger iron isotopic variations, with δ57Fe ranging from 0.12 to 0.30. The δ57Fe values of minerals in these garnet-bearing pyroxenites also vary widely (?0.25 to 0.08 in olivines, ?0.04 to 0.25 in orthopyroxenes, ?0.07 to 0.31 in clinopyroxenes, 0.07 to 0.48 in spinels and 0.31–0.42 in garnets). In addition, the garnet-bearing pyroxenite shows light δ26Mg (?0.43) relative to the mantle. The δ26Mg of minerals in the garnet-bearing pyroxenite range from ?0.35 for olivine and orthopyroxene, to ?0.34 for clinopyroxene, 0.04 for spinel and ?0.68 for garnet. These measured values stand in marked contrast to calculated equilibrium iron and magnesium isotope fractionation between coexisting mantle minerals at mantle temperatures derived from theory, indicating disequilibrium isotope fractionation. Notably, one phlogopite clinopyroxenite with an apparent later metasomatic overprint has the heaviest δ57Fe (as high as 1.00) but the lightest δ26Mg (as low as ?1.50) values of all investigated samples. Overall, there appears to be a negative co-variation between δ57Fe and δ26Mg in the Hannuoba garnet-bearing pyroxenite and in the phlogopite clinopyroxenite xenoliths and minerals therein. These features may reflect kinetic isotopic fractionation due to iron and magnesium inter-diffusion during melt–rock interaction. Such processes play an important role in producing inter-mineral iron and magnesium isotopic disequilibrium and local iron and magnesium isotopic heterogeneity in the subcontinental mantle.  相似文献   

11.
Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ56Fe values for mantle-derived basaltic magmas (δ56Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ56Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ56Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ56Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ56Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe3+-rich fluids at igneous or near-igneous temperatures; the expected δ56Fe values for Fe2+-bearing fluids are too low to produced the observed positive δ56Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe3+-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ56Fe fenites, but this has yet to be tested.  相似文献   

12.
The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ18O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ18O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The 18O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ18O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) 18O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998  相似文献   

13.
The oxygen isotopic composition was studied in minerals and rocks from the critical zone of the Ioko-Dovyren layered pluton. The δ18O values vary from +5.4 to +6.1‰ in rocks, from +4.8 to +5.8‰ in olivine, from +5.5 to 6.5‰ in pyroxene, and from +5.8 to +6.9‰ in plagioclase and fall into the interval of mantle values for continental mafic and ultramafic rocks. A decrease in δ18O could have been caused by penetration of meteoric water. Postmagmatic (retrograde) oxygen isotopic redistribution in the slowly cooling rocks is responsible for disturbance of oxygen isotope equilibria in the coexisting minerals, which were crystallized from the same magma at a high temperature. The nonequilibrium oxygen isotopic composition in the associated minerals and calculated temperature of the final isotopic equilibration do not contradict the model of “fluid” formation of low-sulfide PGE mineralization in the Ioko-Dovyren layered pluton.  相似文献   

14.
Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ34S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ34S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ34S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of 206Pb/204Pb and 207Pb/204Pb or 208Pb/204Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The 3He/4He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material  相似文献   

15.
A generalized approach for retrieving equilibrium isotope fractionations from natural rocks is proposed in which models of prograde reaction histories and retrograde diffusional exchange are used to identify coexisting minerals with similar isotope closure temperatures. Examples using literature data and new analyses from 32 natural amphibolite-facies schists demonstrate both the feasibility and limitations of obtaining equilibrium oxygen isotope fractionations from minerals in natural rocks. By screening samples according to the theoretical models, natural data are shown to have highly consistent mineral fractionations (±2σ reproducibilities of ±0.16 to 0.54‰) that within uncertainty reproduce experimental determinations among the minerals quartz, biotite, muscovite, and calcic amphibole. This correspondence indicates that the proposed theoretically-based selection criteria improve the likelihood of measuring equilibrium fractionations. The new data further corroborate the expected progressive enrichment of δ18O in the orthosilicates with increasing Al+Si relative to Fe+Mg: Δ(Ky-Grt) ∼1.05‰, Δ(St-Grt) ∼0.6‰, and Δ(St-Cld) ∼0.3‰ at 525–575 °C. In contrast, typical samples that fail to satisfy screening criteria exhibit fractionations involving quartz, biotite, and amphibole that are strongly disequilibrium because of exchange during cooling. Theoretical screening of samples prior to isotope analysis allows robust, independent assessment of theoretical and experimental determinations of equilibrium isotope fractionations. Received: 14 January 1997 / Accepted: 9 March 1998  相似文献   

16.
Li contents and its isotopes of minerals in mantle peridotite xenoliths from late Cretaceous mafic dikes, analyzed in situ by Cameca IMS-1280, reveal the existence of melt/rock interaction in remains of refertilized Archean lithospheric mantle in Qingdao, Jiaodong Peninsula, North China Craton. Two groups of peridotites exist, i.e., low-Mg# lherzolite and high-Mg# harzburgites. The low-Mg# lherzolite has a relatively homogeneous Li concentration (ol: 2.01–2.11 ppm; opx: 1.77–1.88 ppm; cpx: 1.75–1.93 ppm) and Li isotopic composition (δ7Li in ol: 4.2–7.6‰; in opx: 6.0–8.3‰; in cpx: 5.3–8.4‰). The similarity in δ7Li value to the fresh MORB provides further evidence for the argument that the low-Mg# lherzolite could be the fragment of the newly accreted lithospheric mantle. The high-Mg# harzburgites have heterogeneous Li abundances (ol: 0.83–2.09 ppm; opx: 0.92–1.94 ppm; cpx: 1.12–4.89 ppm) and Li isotopic compositions (δ7Li in ol: −0.5 to +11.5‰; in opx: −6.2 to +11.1‰; in cpx: −34.3 to +10.1‰), showing strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The cores of most minerals in these high-Mg# harzburgites have relatively homogeneous δ7Li values, which are higher than those of fresh MORB, but similar to those previously reported for arc lavas. These harzburgites have enriched trace elemental and Sr–Nd isotopic compositions. These observations indicate that in the early Mesozoic the lithospheric mantle beneath the southeastern North China Craton was similar to that in arc settings, which is metasomatized by subducted crustal materials. Extremely low δ7Li preserved in cpxs requires diffusive fractionation of Li isotopes from later-stage melt into the minerals. Thus, the Li data provide further evidence that the Archean refractory lithospheric mantle represented by the high-Mg# harzburgites was refertilized through melt/rock interaction and transformed to the Mesozoic less refractory and incompatible element and Sr–Nd isotopes enriched lithospheric mantle.  相似文献   

17.
Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.  相似文献   

18.
Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ18O values decrease down to values of 12‰ towards the contact with dolostones. This 18O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from 87Sr/86Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with 87Sr/86Sr = 0.7094 near dolomitization fronts. Dolostones have δ18O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (87Sr/86Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ18O values close to dolostones but substantially lower δ13C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with 87Sr/86Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ18O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.  相似文献   

19.
In order to shed light on upper crustal differentiation of mantle-derived basaltic magmas in a subduction zone setting, we have determined the mineral chemistry and oxygen and hydrogen isotope composition of individual cumulus minerals in plutonic blocks from St. Vincent, Lesser Antilles. Plutonic rock types display great variation in mineralogy, from olivine–gabbros to troctolites and hornblendites, with a corresponding variety of cumulate textures. Mineral compositions differ from those in erupted basaltic lavas from St. Vincent and in published high-pressure (4–10 kb) experimental run products of a St. Vincent high-Mg basalt in having higher An plagioclase coexisting with lower Fo olivine. The oxygen isotope compositions (δ18O) of cumulus olivine (4.89–5.18‰), plagioclase (5.84–6.28‰), clinopyroxene (5.17–5.47‰) and hornblende (5.48–5.61‰) and hydrogen isotope composition of hornblende (δD = −35.5 to −49.9‰) are all consistent with closed system magmatic differentiation of a mantle-derived basaltic melt. We employed a number of modelling exercises to constrain the origin of the chemical and isotopic compositions reported. δ18OOlivine is up to 0.2‰ higher than modelled values for closed system fractional crystallisation of a primary melt. We attribute this to isotopic disequilibria between cumulus minerals crystallising at different temperatures, with equilibration retarded by slow oxygen diffusion in olivine during prolonged crustal storage. We used melt inclusion and plagioclase compositions to determine parental magmatic water contents (water saturated, 4.6 ± 0.5 wt% H2O) and crystallisation pressures (173 ± 50 MPa). Applying these values to previously reported basaltic and basaltic andesite lava compositions, we can reproduce the cumulus plagioclase and olivine compositions and their associated trend. We conclude that differentiation of primitive hydrous basalts on St. Vincent involves crystallisation of olivine and Cr-rich spinel at depth within the crust, lowering MgO and Cr2O3 and raising Al2O3 and CaO of residual melt due to suppression of plagioclase. Low density, hydrous basaltic and basaltic andesite melts then ascend rapidly through the crust, stalling at shallow depth upon water saturation where crystallisation of the chemically distinct cumulus phases observed in this study can occur. Deposited crystals armour the shallow magma chamber where oxygen isotope equilibration between minerals is slowly approached, before remobilisation and entrainment by later injections of magma.  相似文献   

20.
The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ18O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ34S = +0.8‰ to +5.9‰; δ18O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ13C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ34S (+1.8‰ to +5.0‰), δ18O (+10.1‰ to +12.5‰) and δ13C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ34S = +0.8‰ to +3.9‰; δ18O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ34S ≥ +29‰, δ18O = 0.1‰ and δ13C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.  相似文献   

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