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1.
Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ7Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ7Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ7Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ7Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ7Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ7Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ7Li), while non mantle-like, low δ7Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.  相似文献   

2.
In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ56/54FeIRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ56/54FeM–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ56/54FeIRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ7Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.  相似文献   

3.
The Ilímaussaq intrusion, South Greenland, provides an exceptional test case for investigating the changes of stable Fe isotope fractionation of solidus phases with changes in the Fe3+/∑Fe ratio of an evolving melt. The intrusion comprises a sequence of four melt batches that were fed from the same parental alkali basaltic magma. Differentiation produced cumulate rocks that range from augite syenite (phase I) over peralkaline granite (phase II) to agpaitic syenites (phases IIIa and IIIb). Fe3+/∑Fe ratios in amphiboles increase substantially from phase I to phase II and III rocks and mark a major change in the parental magma composition from augite syenites to peralkaline granites and agpaitic syenites. Before this transition, olivine, clinopyroxene, and amphibole in augite syenite, the most primitive rock type in the Ilímaussaq Complex, have a uniform Fe isotope composition that is identical to that of the bulk of igneous crustal rocks and approximated by the average isotopic composition of basalts (δ56/54FeIRMM-014 = 0.072 ± 0.046‰). After the transition, amphiboles in the peralkaline granites and agpaitic syenites yield significantly heavier Fe isotope compositions with δ56/54FeIRMM-014 values ranging from 0.123 to 0.237‰. Contamination of the Ilímaussaq magma by ongoing crustal assimilation as cause for this increase can be excluded on the grounds of Nd isotope data. Large-scale metasomatic overprint with an external fluid can also be dismissed based on amphibole O and Li isotope systematics. Rather, the increase towards heavy Fe isotope compositions most likely reflects the change in chemical compositions of amphiboles (calcic in augite syenite to sodic in the agpaitic syenites) and their Fe3+/ΣFe ratios that mirror changes in the chemical composition of the melt and its oxygen fugacity. A sensitive adjustment of equilibrium Fe isotope fractionation factors to amphibole ferric/ferrous ratios is also supported by beta-factors calculated from Mössbauer spetroscopy data. Comparison of the measured isotope fractionation between clinopyroxene and amphibole with that predicted from Mössbauer data reveal Fe isotope systematics close to equilibrium in augite syenites but Fe isotopic disequilibrium between these two phases in phase IIIa agpaitic syenites. These results are in agreement with O and Li isotope systematics. While amphiboles in all Ilímaussaq lithologies crystallized at temperatures between 650 and 850 °C, textural evidence reveals later clinopyroxene crystallization at temperatures as low as 300–400 °C. Therefore, isotopic equilibrium at crystallization conditions between these two phases can not be expected, but importantly, subsolidus reequilibration can also be dismissed.  相似文献   

4.
The Han-Xing iron mineralization in the central North China Craton is a typical Fe skarn deposit associated with altered diorites. Here we report the Fe isotopic compositions of whole rocks and mineral separates from this deposit with a view to evaluate the Fe isotope fractionation during the formation of Fe skarn deposit, and to constrain the metal source. The Fe isotopes show a large variation both in whole rocks and mineral separates. Altered diorites show a wide range in δ56Fe values (− 0.07‰ to + 0.21‰ relative to the Fe isotope standard IRMM-014) which positively correlate with their TFe2O3/TiO2 ratios (Fe2O3 and FeO calculated as TFe2O3). The positive correlation indicates that heavy Fe isotopes were preferentially leached from diorites during the skarn-type alteration. Among the metallic minerals, pyrite and pyrrhotite are isotopically heavier (+ 0.12‰ to + 0.48‰) than the magnetite (+ 0.07‰ to + 0.21‰). Fe isotope fractionation between mineral pairs demonstrates that magnetite did not attain Fe isotopic equilibrium with pyrite and pyrrhotite, whereas pyrite and pyrrhotite might have attained isotopic equilibrium. Petrological observations and major element data also suggest that iron was leached from the diorites during the skarn-type alteration. If the leached iron provides the main Fe budget of the Han-Xing Fe skarn deposit, magnetite in ores would be isotopically heavier than the unaltered diorite. However, our results are in contrast with the magnetite being isotopically lighter than the unaltered diorite. This suggests that the major Fe source of the Han-Xing Fe skarn deposit is not from the leaching of diorites, and might be from magmatic fluid which is isotopically lighter than the silicate melt. Our data demonstrate that Fe isotopes can be used as important tracers in deciphering the metal source of Fe skarn deposits.  相似文献   

5.
Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ7Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ7Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H2O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.  相似文献   

6.
Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (65Cu/63Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (56Fe/54Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ65Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ56Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ56Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.  相似文献   

7.
Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ7Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ7Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ7Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ7Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ7Li, the carbonatite and silicate melts produced remarkably contrasting δ7Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ7Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.  相似文献   

8.
We report Lithium (Li) concentrations and isotopic compositions for co-existing olivine, orthopyroxene (opx), and clinopyroxene (cpx) mineral separates from depleted and metasomatised peridotite xenoliths hosted by basaltic lavas from northwestern Ethiopian plateau (Gundeweyn area). The peridotites contain five lherzolites and one harzburgite and are variably depleted and enriched in LREE relative to HREE. In both depleted and enriched lherzolites, Li is preferentially incorporated into olivine (2.4-3.3 ppm) compared to opx (1.4-2.1 ppm) and cpx (1.4-2.0 ppm) whereas the Li contents of olivines (5.4 ppm) from an enriched harzburgiteare higher than those of lherzolites. Olivines from the samples show higher Li abundances than normal mantle olivines (1.6-1.9 ppm) indicating the occurrence of Li enrichments through melt-preroditite interaction. The average δ7 Li values range from +2.2 to +6.0‰ in olivine, from -0.1 to +2.0‰ in opx and from -4.4 to -0.9‰ in cpx from the lherzolites. The Li isotopic composition (3.5‰) of olivines from harzburgite fall within the range of olivine from lherzolites but the opxs show low in δ7Li (-2.0‰). Overall Li isotopic compositions of olivines from the peridotites fall within the range of normal mantle olivine, δ7Li values of ~+4±2‰ within uncertainty, reflecting metasomatism (enrichment) of the peridotites by isotopically heavy Li-rich asthenospheric melt. Li isotope zonation is also observed in most peridotite minerals. Majority of olivine grains display isotopically heavy cores and light rims and the reverse case is observed for some olivine grains. Orthopyroxene and clinopyroxene grains show irregular distribution in δ7Li. These features of Li isotopic compositions within and between grains in the samples reflect the effect of diffusion-driven isotopic fractionation during meltperidotite interaction and cooling processes.  相似文献   

9.
Lithium-rich brine within the sub-surface of the Salar del Hombre Muerto (SHM) salt pan in the Andes of northwestern Argentina has a chemical and isotopic composition which is consistent with Li derived from several sources: the modern halite saturated lagoon, Li-rich salts and brines formed recently, and dissolution of halite which precipitated from ancient saline lakes. SHM lies in the closed basin that includes part of the massive Cerro Galán caldera which is drained by the Río los Patos, which is responsible for 90% of surface runoff into the salar. The low Li isotope composition, +3.4‰, of this river is consistent with significant contributions of geothermal spring water. As water drains through the volcaniclastic deposits which cover a large proportion of the basin, Li removal, as indicated by decreasing Li/Na, occurs but without significant isotope fractionation. This indicates a mechanism of surface sorption onto smectite or ferrihydrite rather than Li incorporation into octahedral structural sites of clays. These observations suggest that conditions in this high altitude desert have limited the dilution of hydrothermal spring water as well as the formation of clay minerals, which jointly have allowed the Li resource to accumulate rapidly. Changes in climate on a multi-millennial time scale, specifically in the hydrologic budget, have resulted in solute accumulation rates that have been variable through time, and decoupled Li and Na fluxes. Inflow to the salar under modern conditions has high Li/Na (7.9 × 10−3 by wt) with δ7Li indistinguishable from basement rocks (−0.3‰ to +6.4‰), while under pluvial climate conditions the Li/Na of the saline lake was 40 times lower than the modern lagoon (0.1–0.3 × 10−3 compared to 10.6–13.4 × 10−3) with slightly higher δ7Li, +6.9‰ to +12.3‰, reflecting the uptake of 6Li into secondary minerals which formed under a wetter climate.  相似文献   

10.
Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ74Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ74Ge. Spex and Merck standard solutions yield mean δ74Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ74Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ74Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ74Gepyrite < δ74Gesphalerite < δ74Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.  相似文献   

11.
Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad29–100Gr0–68) and diopside (Di54–100Hd0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (87Sr/86Sr)i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (87Sr/86Sr)i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ34S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ34S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.  相似文献   

12.
The Haobugao Zn–Fe deposit is a typical skarn deposit located in the southern part of the Great Xing’an Range that hosts polymetallic mineralization over a large region. The main ore minerals at the deposit include sphalerite, magnetite, galena, chalcopyrite and pyrite, and the main gangue minerals include andradite, grossular garnet, hedenbergite, diopside, ilvaite, calcite and quartz. There are broadly two mineralizing periods represented by the relatively older skarn and younger quartz–sulfide veins. In detail, there are five metallogenic stages consisting of an early skarn, late skarn, oxide, early quartz–sulfide, and late quartz–sulfide–calcite stages. Electron microprobe analyses show that the garnet at the deposit varies in composition from And97.95Gro0.41Pyr1.64 to And30.69Gro66.69Pyr2.63, and pyroxene is compositionally in the diopside–hedenbergite range (i.e. Di90.63Hd8.00Jo1.37–Hd88.98Di4.53Jo6.49). Petrographic observations and electron microprobe analyses indicate that the sphalerite has three generations ([Zn0.93Fe0.08]S–[Zn0.75Fe0.24]S). The Zn associated with the first generation sphalerite replaced Cu and Fe of early xenomorphic granular chalcopyrite (i.e. [Cu1.01Fe1.03]S2–[Cu0.99Fe0.99]S2), and part of the first generation sphalerite is coeval with late chalcopyrite (i.e. [Cu0.96Fe0.99Zn0.03]S2–[Cu1.00Fe1.03Zn0.01]S2). Magnetite has a noticeable negative Ce anomaly (δCe = ∼0.17 to 0.54), which might be a result of the oxidized ore-fluid. Thirty δ34SV-PDB analyses of sulfides from the ore range from −2.3 to −0.1‰ in value, which are indicative of a magmatic source. The δ13C‰ and δ18O‰ values for calcite from the ore formed at quartz–sulfide–calcite stage vary from −9.9 to −5.5‰ and from −4.2 to 1.1‰, respectively, contrasting with δ13C‰ (2.9–4.8‰) and δ18O‰ (9.8–13.9‰) values for calcite from marble. It is suggested that the ore-forming fluid associated with late stage of mineralization was predominantly magmatic in origin with some input of local meteoric water.Molybdenite from the Haobugao deposit defines an isochron age of 142 ± 1 Ma, which is interpreted as the mineralization age being synchronous, within error, with the zircon U–Pb ages of 140 ± 1, 141 ± 2, and 141 ± 1 Ma for granite at the deposit. These data and characteristics of lithology and mineralization further show that the Zn–Fe mineralization is temporally and spatially related to the emplacement of granite in an extensional tectonic setting during the Mesozoic.  相似文献   

13.
The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe3 +–Al3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ11B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe3 +–Al3 + substitution) and δ11B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ11B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ11B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ34SVCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ34SVCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ34SVCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ34SVCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ65CuNBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ65CuNBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ34SVCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.  相似文献   

14.
The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270 km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7 million tonnes of sulfide ores grading 0.54 to 8.94 wt.% Pb and 1.09 to 26.64 wt.% Zn. Calcite samples have δ13CPDB and δ18OSMOW values ranging from − 3.1 to + 2.5‰ and + 18.8 to + 26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ13CPDB vs. δ18OSMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ34SCDT values of sphalerite and galena samples range from + 18.9 to + 20.3‰ and + 15.6 to + 17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ34SCDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292 °C, consistent with previous fluid inclusion studies. Temperatures above 100 °C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ66Zn values ranging from 0.00 to + 0.55‰ (mean + 0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ66Zn values ranging from 0.00 to + 0.07‰, + 0.12 to + 0.23‰, and + 0.29 to + 0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a 207Pb/204Pb vs. 206Pb/204Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have 87Sr/86Sr200 Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.  相似文献   

15.
The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ65Cu values (δ65Cu = ((65Cu/63Cu)sample/(65Cu/63Cu)standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ65Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ65Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.  相似文献   

16.
Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C2+ HC. Its dryness coefficient (C1/C1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH4 and heavy hydrocarbons (C2+) and higher contents of non-hydrocarbons (e.g. CO2), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ13C1: −45‰ to −36‰) and heavier values for ethane (δ13C2: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ13C1 = −36‰ to −45‰ and δ13C2 = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ13CCO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ13CCO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO2 captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO2. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.  相似文献   

17.
Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ34SCDT values ranging from 0.2 to 5.0‰. Although δ34SCDT and δ114/110Cd values in sphalerites have no regular spatial variations, the δ34SCDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ34S∑S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.  相似文献   

18.
Carbon (δ13CPDB) and oxygen (δ18OSMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ13Cpdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ18O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ13C∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ18OH2O from 6.8‰ to 25.9‰, respectively. Carbonate δ13C and fluid δ13C∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO2 with δ13C values similar to or more enriched than parent rock, the carbonate or fluid δ13C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO2 or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.  相似文献   

19.
The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe3+/(Fe3+ + Cr + Al) (>70), high 100 × Fe2+/(Fe2+ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO2 contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe2+/(Mg + Fe2+) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.  相似文献   

20.
This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shellE. desertorum were analyzed for carbonate composition and isotopic composition (δ18O, δ13C). The plants and organic matterE. desertorum were analyzed for organic carbon content and δ13C. The soil carbonate, consisting of calcite plus minor dolomite, has δ18O values from −3.19 to −1.78‰ and δ13C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ13C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shellE. desertorum is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ18Omean = −0.28 ± 0.22‰; δ13Cmean = −4.46 ± 0.58‰). Most of the δ18O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matterE. desertorum varies only slightly in bulk organic carbon δ13C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ13C values (−17.32‰) observed between shellE. desertorum carbonate and organic matterE. desertorum exceeds the value expected for vegetation input, and implies that 30% of carbon in the shellE. desertorum carbonate comes from the consumption of limestone material.  相似文献   

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