Iron Isotope Compositions of Coexisting Sulfide and Silicate Minerals in Sudbury-Type Ores from the Jinchuan Ni-Cu Sulfide Deposit: A Perspective on Possible Core-Mantle Iron Isotope Fractionation

Many studies have shown that the average iron (Fe) isotope compositions of mantle-derived rocks, mantle peridotite and model mantle are close to those of chondrites. Therefore, it is considered that chondrite values represent the bulk Earth Fe isotope composition. However, this is a brave assumption because nearly 90% of Fe of the Earth is in the core, where its Fe isotope composition is unknown, but it is required to construct bulk Earth Fe isotope composition. We approach the problem by assuming that the Earth’s core separation can be approximated in terms of the Sudbury-type Ni-Cu sulfide mineralization, where sulfide-saturated mafic magmas segregate into immiscible sulfide liquid and silicate liquid. Their density/buoyancy controlled stratification and solidification produced net-textured ores above massive ores and below disseminated ores. The coexisting sulfide minerals (pyrrhotite (Po) > pentlandite (Pn) > chalcopyrite (Cp)) and silicate minerals (olivine (Ol) > orthopyroxene (Opx) > clinopyroxene (Cpx)) are expected to hold messages on Fe isotope fractionation between the two liquids before their solidification. We studied the net-textured ores of the Sudbury-type Jinchuan Ni-Cu sulfide deposit. The sulfide minerals show varying δ56Fe values (−1.37–−0.74‰ (Po) < 0.09–0.56‰ (Cp) < 0.53–1.05‰ (Pn)), but silicate minerals (Ol, Opx, and Cpx) have δ56Fe values close to chondrites (δ56Fe = −0.01 ± 0.01‰). The heavy δ56Fe value (0.52–0.60‰) of serpentines may reflect Fe isotopes exchange with the coexisting pyrrhotite with light δ56Fe. We obtained an equilibrium fractionation factor of Δ56Fesilicate-sulfide ≈ 0.51‰ between reconstructed silicate liquid (δ56Fe ≈ 0.21‰) and sulfide liquid (δ56Fe ≈ −0.30‰), or Δ56Fesilicate-sulfide ≈ 0.36‰ between the weighted mean bulk-silicate minerals (δ56Fe[0.70ol,0.25opx,0.05cpx] = 0.06‰) with weighted mean bulk-sulfide minerals (δ56Fe ≈ −0.30‰). Our study indicates that significant Fe isotope fractionation does take place between silicate and sulfide liquids during the Sudbury-type sulfide mineralization. We hypothesize that significant iron isotope fractionation must have taken place during core–mantle segregation, and the bulk Earth may have lighter Fe isotope composition than chondrites although Fe isotope analysis on experimental sulfide-silicate liquids produced under the varying mantle depth conditions is needed to test our results. We advocate the importance of further research on the subject. Given the close Fe-Ni association in the magmatic mineralization and the majority of the Earth’s Ni is also in the core, we infer that Ni isotope fractionation must also have taken place during the core separation that needs attention.

The geochemistry of thallium and its isotopes in rare-element pegmatites

The Tl isotopic and trace element composition of K-feldspar, mica, pollucite and pyrite from 13 niobium-yttrium-fluorine (NYF)-type and 14 lithium-cesium-tantalum (LCT)-type rare-element pegmatites was investigated. In general, the epsilon-205Tl values for K-feldspar in NYF- and LCT-type pegmatites increases with increasing magmatic fractionation. Both NYF and LCT pegmatites display a wide range in epsilon-205Tl (-4.25 to 9.41), which complicates attempts to characterize source reservoirs. We suggest 205Tl-enrichment during pegmatite crystallization occurs as Tl partitions between the residual melt and a coexisting aqueous fluid or flux-rich silicate liquid. Preferential association of 205Tl with Cl in the immiscible aqueous fluid may influence the isotopic character of the growing pegmatite minerals. Subsolidus alteration of K-feldspar by aqueous fluids, as indicated by the redistribution of Cs in K-feldspar, resulted in epsilon-205Tl values below the crustal average (-2.0 epsilon-205Tl). Such low epsilon-205Tl values in K-feldspar is attributed to preferential removal and transport of 205Tl by Cl-bearing fluids during dissolution and reprecipitation. The combination of thallium isotope and trace element data may be used to examine late-stage processes related to rare-element mineralization in some pegmatites. High epsilon-205Tl and Ga in late-stage muscovite appears to be a favorable indicator of rare-element enrichment LCT pegmatites and may be a useful exploration vector.

Structural and Dynamics Heterogeneity in Sodium Silicate Liquid

Liquid Na2O-4SiO2 has been constructed by molecular dynamics simulation at 1873 K, ambient pressure under periodic boundary conditions. To clarify the local environment of atoms we apply the oxygen simplex (OS) which is characterized by the size, forming oxygen atom types and the number of sodium located inside the OS. The simulation shows that the liquid comprises the Si-O network and sodium atoms are distributed through different type OSs forming by four O atoms. The number of sodium in particular simplex depends on the size and types of OS. There are five types of OS corresponding to values of n=0÷4. Here n is number of bridge oxygens which an OS passed through. We also found that numerous OSs connected to each other form a long channel where hundreds sodium atoms move. The observed distribution of sodium through Si-O network clearly indicates the structural and dynamics heterogeneity in sodium silicate liquid.

Evidence for Silicate–Liquid Immiscibility in Monzonites and Petrogenesis of Associated Fe–Ti–P-rich rocks: Example from the Raftsund Intrusion, Lofoten, Northern Norway

The 1800 Ma monzonitic to syenitic Raftsund intrusion is the largest intrusive body of the Lofoten–Vesterålen anorthosite–mangerite–charnockite–granite (AMCG) suite. It is composed of three units that can be differentiated based on their textures. This study focuses on the most voluminous, predominantly equigranular, unit consisting of a pigeonite–augite syenite and a fayalite–augite monzonite. The pigeonite–augite syenite is associated with centimeter-scale to hundred-meter scale occurrences of Fe–Ti–P-rich rocks that display sharp to gradational contacts with the surrounding syenite. Iron–Ti–P-rich rocks consist of augite, Fe-rich olivine ± partly inverted pigeonite, apatite, ilmenite, titanomagnetite and sparse pyrrhotite, hornblende and biotite. Partly resorbed ternary feldspar crystals are common toward the contact with the syenite. Microtextures, such as symplectites, encountered at the contact between the syenite and the Fe–Ti–P-rich rocks indicate local disequilibrium between the two rock types. The Fe–Ti–P-rich rocks show large compositional variations but overall are enriched in Ca, Zn, Sc and rare earth elements in addition to Fe, Ti and P compared with the host syenite. Field evidence, whole-rock compositions and textural relationships all suggest that that silicate–liquid immiscibility was involved in the genesis of the Fe–Ti–P-rich rocks. These are interpreted to represent Fe-rich unmixed melts, whereas the syenite is inferred to originate from the crystallization of conjugate Si-rich immiscible melt. The existence of an Fe-rich melt is further supported by the high trace element content of augite from the Fe–Ti–P-rich rocks, showing that they grew from a melt enriched in elements such as Sc and Ti. The fayalite–augite monzonite also displays textural and chemical evidence of silicate liquid immiscibility resulting in unusually variable Zr contents (few hundred ppm to more than 3000 ppm) and the presence of abundant zircon and allanite restricted to millimeter- to centimeter-scale Fe-rich mineral clusters. The most Fe-rich and Si-poor rocks are interpreted to represent the larger proportion of the Fe-rich melt. Liquid immiscibility can be identified at various scales in the pigeonite–augite syenite, from millimeter-size clusters to large-scale bodies, up to hundreds of meters in size, indicating various degrees of separation and coalescence of the Fe-rich melt in the intrusion. The immiscible liquids in the fayalite–augite monzonite consist of an emulsion, with small millimeter- to centimeter-scale droplets of Fe-rich melt, whereas in the pigeonite–augite syenite, Fe-rich melt pockets were able to coalesce and form larger pods. The difference between the two units either results from earlier onset of immiscibility in the pigeonite–augite syenite or reflects a difference in the degree of polymerization of the melt at the time of unmixing. This study emphasizes the importance of silicate–liquid immiscibility in the evolution of intermediate to felsic alkalic ferroan systems and provides a series of arguments that can be used to identify the process in such systems.