Kinetic isotope effect during reduction of iron from a silicate melt

Iron isotopic compositions measured in chondrules from various chondrites vary between δ⁵⁷Fe/⁵⁴Fe = +0.9‰ and −2.0‰, a larger range than for igneous rocks. Whether these compositions were inherited from chondrule precursors, resulted from the chondrule-forming process itself or were produced by later parent body alteration is as yet unclear. Since iron metal is a common phase in some chondrules, it is important to explore a possible link between the metal formation process and the observed iron isotope mass fractionation. In this experimental study we have heated a fayalite-rich composition under reducing conditions for heating times ranging from 2 min to 6 h. We performed chemical and iron isotope analyses of the product phases, iron metal and silicate glass. We demonstrated a lack of evaporation of Fe from the silicate melt in similar isothermal experiments performed under non-reducing conditions. Therefore, the measured isotopic mass fractionation in the glass, ranging between −0.32‰ and +3.0‰, is attributed to the reduction process. It is explained by the faster transport of lighter iron isotopes to the surface where reduction occurs, and is analogous to kinetic isotope fractionation observed in diffusion couples [Richter, F.M., Davis, A.M., Depaolo, D.J., Watson, E.B., 2003. Isotope fractionation by chemical diffusion between molten basalt and rhyolite. Geochim. Cosmochim. Acta67, 3905-3923]. The metal phase contains 90-99.8% of the Fe in the system and lacks significant isotopic mass fractionation, with values remaining similar to that of the starting material throughout. The maximum iron isotope mass fractionation in the glass was achieved within 1 h and was followed by an isotopic exchange and re-equilibration with the metal phase (incomplete at ∼6 h). This study demonstrates that reduction of silicates at high temperatures can trigger iron isotopic fractionation comparable in its bulk range to that observed in chondrules. Furthermore, if metal in Type I chondrules was formed by reduction of Fe silicate, our observed isotopic fractionations constrain chondrule formation times to approximately 60 min, consistent with previous work.     

Germanium isotope geochemistry: analysis,fractionation mechanisms and geochemical tracing

<正>Introduction Since Ge isotope is a new nontraditional isotope,the accumulated Ge isotope literatures are quite limited.The available researches mainly focused on two aspects:(1)the measurement of Ge isotopic compositions of geological and extraterrestrial materials,such as igneous rocks,marine sediments,seafloor hydrothermal fluids,hydrothermal Fe-oxyhydroxides,terrestrial high-temperature geothermal fluids,sphalerite,and iron meteorites;and(2)theoretical prediction of germanium isotope fractionation.     

Oxygen isotopic signature of 4.4-3.9 Ga zircons as a monitor of differentiation processes on the Moon

We report oxygen isotopic compositions for 14 zircon grains from a sample of sawdust from lunar breccia 14321. The zircons range in age from ∼4.4 to 3.9 Ga and in U and Th content from a few to several hundred ppm. As such these grains represent a range of possible source rocks, from granophyric to mafic composition, and cover the total age range of the major initial lunar bombardment. Nevertheless, results show that the oxygen isotopic compositions of the zircons fall within a narrow range of δ¹⁸O of about 1 per mil and have δ¹⁸O values indistinguishable from those observed for terrestrial mid-ocean ridge basalts confirming the coincidence of lunar and Earth oxygen isotopic compositions. In the δ¹⁷O vs. δ¹⁸O, coordinates data form a tight group with a limited trend on the terrestrial fractionation line. The zircon oxygen isotopes show minimal evidence of the extreme and variable mineral differentiation and element fractionation that have contributed to the formation of their parent rocks.     

Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC‐ICP‐MS

Although initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass‐dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two‐stage chromatography procedure, Ni isotope ratios were measured by MC‐ICP‐MS and were corrected for instrumental mass bias using a double‐spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous‐ and mantle‐derived rocks displayed a restricted range of δ^60/58Ni values between ?0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO‐1), coal (CLB‐1) and a metal‐contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite‐hosted Ni‐rich sulfides varied from ?0.10 to ?1.03‰.     

On the iron isotope heterogeneity of lithospheric mantle xenoliths: implications for mantle metasomatism, the origin of basalts and the iron isotope composition of the Earth

With the aim to better understand the cause of the iron isotope heterogeneity of mantle-derived bulk peridotites, we compared the petrological, geochemical and iron isotope composition of four xenolith suites from different geodynamic settings; sub-arc mantle (Patagonia); subcontinental lithospheric mantle (Cameroon), oceanic mantle (Kerguelen) and cratonic mantle (South Africa). Although correlations were not easy to obtain and remain scattered because these rocks record successive geological events, those found between δ⁵⁷Fe, Mg#, some major and trace element contents of rocks and minerals highlight the processes responsible for the Fe isotope heterogeneity. While partial melting processes only account for moderate Fe isotope variations in the mantle (<0.2 ‰, with bulk rock values yielding a range of δ⁵⁷Fe ± 0.1 ‰ relative to IRMM-14), the main cause of Fe isotope heterogeneity is metasomatism (>0.9 ‰). The kinetic nature of rapid metasomatic exchanges between low viscosity melts/fluids and their wall-rocks peridotite in the mantle is the likely explanation for this large range. There are a variety of responses of Fe isotope signatures depending on the nature of the metasomatic processes, allowing for a more detailed study of metasomatism in the mantle with Fe isotopes. The current database on the iron isotope composition of peridotite xenoliths and mafic eruptive rocks highlights that most basalts have their main source deeper than the lithospheric mantle. Finally, it is concluded that due to a complex geological history, Fe isotope compositions of mantle xenoliths are too scattered to define a mean isotopic composition with enough accuracy to assess whether the bulk silicate Earth has a mean δ⁵⁷Fe that is chondritic, or if it is ~0.1 ‰ above chondrites as initially proposed.     

High precision iron isotope measurements of meteoritic material by cold plasma ICP-MS

The first cold plasma ICP-MS (inductively coupled plasma mass spectrometer) Fe isotope study is described. Application of this technique to the analyses of Fe isotopes in a number of meteorites is also reported. The measurement technique relies on reduced temperature operation of the ICP source to eliminate pervasive molecular interferences from Ar complexes associated with conventional ICP-MS. Instrumental mass bias corrections are performed by sample-standard bracketing and using Cu as an external mass bias drift monitor. Repeated measurements of a terrestrial basalt reference sample indicate an external reproducibility of ± 0.06 ‰ for δ⁵⁶Fe and ± 0.25 ‰ for δ⁵⁸Fe (1 σ). The measured iron isotopic compositions of various bulk meteorites, including irons, chondrites and pallasites are identical, within error, to the composition of our terrestrial basalt reference sample suggesting that iron mass fractionation during planet formation and differentiation was non-existent. Iron isotope compositions measured for eight chondrules from the unequilibrated ordinary chondrite Tieschitz range from −0.5 ‰ < δ⁵⁶Fe_chondrules < 0.0 ‰ relative to the terrestrial/meteorite average. Mechanisms for fractionating iron in these chondrules are discussed.     

Fe isotope systematics of coexisting amphibole and pyroxene in the alkaline igneous rock suite of the Ilímaussaq Complex,South Greenland

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 (δ^56/54Fe_IRMM-014 = 0.072 ± 0.046‰). After the transition, amphiboles in the peralkaline granites and agpaitic syenites yield significantly heavier Fe isotope compositions with δ^56/54Fe_IRMM-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.     

Rubidium Isotope Ratios of International Geological Reference Materials

In this study we determined rubidium isotope ratios in twenty-one commonly used international geological reference materials, including igneous, sedimentary and metamorphic rocks, as well as an IAPSO seawater reference material. All δ⁸⁷Rb results were obtained relative to the NIST SRM 984 reference material. For most reference materials, Rb was purified using a single column loaded with Sr-spec resin. For reference materials containing low Rb but high mass fractions of matrix elements (such as basic rock and seawater), Rb was purified using two-column chromatography, with the first column packed with AGMP-50 resin and the second column packed with Sr-spec resin. Two methods for instrumental mass bias correction, sample-standard bracketing (SSB) mode, and the combined sample-standard bracketing and Zr internal normalisation (C-SSBIN) method, were compared for Rb isotopic measurements by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The long-term reproducibility of Rb isotopic measurements using both methods was similar, better than 0.06‰ (2s, standard deviation) for NIST SRM 984. Significant Rb isotopic fractionation was observed among the reference materials, with an overall variation in δ⁸⁷Rb values of approximately 0.5‰. The δ⁸⁷Rb values of igneous rocks ranged from -0.28‰ to +0.06‰, showing a trend from heavier isotopic compositions in mafic rocks to lighter δ⁸⁷Rb values in the more evolved felsic rocks. The sedimentary and metamorphic rocks had Rb isotope ratios similar to those of igneous rocks. The δ⁸⁷Rb values of the reference materials related to low-temperature geological processes showed a wider range than those of high-temperature processes. Notably, the IAPSO seawater reference material had a δ⁸⁷Rb value of +0.14‰, which deviated from that of igneous rocks, and represents the heaviest reservoir of Rb isotopes found thus far on Earth. The comprehensive dataset presented here has the potential to serve for quality assurance purposes, and provide a framework for interlaboratory comparisons of Rb isotope ratios.     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

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.     

Iron isotope fractionation during skarn-type alteration: Implications for metal source in the Han-Xing iron skarn deposit

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.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

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 Δ⁵⁶Fe_{clinopyroxene-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 Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-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.     

Iron-Molybdenum Isotopes and the Chemical Evolution of Ancient-Oceans

Iron(Fe) is abundant in nature while molybdenum(Mo) is the most abundant transition metal in seawater. Due to their high sensitivity to the redox state of the environment, the isotopic compositions of Fe and Mo as well as variations have been widely used to probe the redox conditions and the evolution of ancient ocean chemistry in favor of improved analytical techniques. Here, we summarized isotopic fractionation mechanisms and natural distribution of both iron and molybdenum isotopes, and further we summarized and partially reinterpreted the redox evolution of ancient oceans through time based on available Fe-Mo data compiled in this study. The process that causes the largest iron isotope fractionation is redox reaction and the iron in oxidation state is generally enriched in ⁵⁶Fe. Biotic and abiotic pyrite formations also produce a large Fe isotope fractionations. Isotopic fractionation of molybdenum in seawater is mainly caused by the adsorption process of dissolved Mo onto ferromanganese oxides or hydroxides in sediments. Fe-Mn (hydro)oxides tend to adsorb isotopically light molybdenum resulting in the isotopic composition of Mo in seawater heavier. However, the Mo sinks in euxinic settings cause almost no molybdenum isotope fractionation. The Fe Mo isotope isotopic records through geological timegenerally suggest similar ocean redox evolution: Oceans older than 2.3 Ga was mainly dominated by ferruginous condition, and there was a slight increase in oxygen content between 2.6 and 2.5 Ga. Earth’s surface was initially oxidized during 2.3 to 1.8 Ga, during which euxinic deposition of sulfide was elevated. Euxinic waters may have expanded greatly between 1.8 and 0.8 Ga, and after that, Earth’s surface had being gradually oxidized and the euxinic waters shrank substantially.Finally, suggestions are proposed for further work on the Fe-Mo isotope research in the context of ancient ocean chemistry.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

An Fe isotope study of ordinary chondrites

The Fe isotope composition of ordinary chondrites and their constituent chondrules, metal and sulphide grains have been systematically investigated. Bulk chondrites fall within a restricted isotopic range of <0.2‰ δ⁵⁶Fe, and chondrules define a larger range of >1‰ (−0.84‰ to 0.21‰ relative to the IRMM-14 Fe standard). Fe isotope compositions do not vary systematically with the very large differences in total Fe concentration, or oxidation state, of the H, L, and LL chondrite classes. Similarly, the Fe isotope compositions of chondrules do not appear to be determined by the H, L or LL classification of their host chondrite. This may support an origin of the three ordinary chondrite groups from variable accretion of identical Fe-bearing precursors.A close relationship between isotopic composition and redistribution of Fe during metamorphism on ordinary chondrite parent bodies was identified; the largest variations in chondrule compositions were found in chondrites of the lowest petrologic types. The clear link between element redistribution and isotopic composition has implications for many other non-traditional isotope systems (e.g. Mg, Si, Ca, Cr). Isotopic compositions of chondrules may also be determined by their melting history; porphyritic chondrules exhibit a wide range in isotope compositions whereas barred olivine and radial pyroxene chondrules are generally isotopically heavier than the ordinary chondrite mean. Very large chondrules preserve the greatest heterogeneity of Fe isotopes.The mean Fe isotope composition of bulk ordinary chondrites was found to be −0.06‰ (±0.12‰ 2 SD); this is isotopically lighter than the terrestrial mean composition and all other published non-chondritic meteorite suites e.g. lunar and Martian samples, eucrites, pallasites, and irons. Ordinary chondrites, though the most common meteorites found on Earth today, were not the sole building blocks of the terrestrial planets.     

Ancient geochemical cycling in the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal Craton

Variations in the isotopic composition of Fe in Late Archean to Early Proterozoic Banded Iron Formations (BIFs) from the Transvaal Supergroup, South Africa, span nearly the entire range yet measured on Earth, from –2.5 to +1.0‰ in ⁵⁶Fe/⁵⁴Fe ratios relative to the bulk Earth. With a current state-of-the-art precision of ±0.05‰ for the ⁵⁶Fe/⁵⁴Fe ratio, this range is 70 times analytical error, demonstrating that significant Fe isotope variations can be preserved in ancient rocks. Significant variation in Fe isotope compositions of rocks and minerals appears to be restricted to chemically precipitated sediments, and the range measured for BIFs stands in marked contrast to the isotopic homogeneity of igneous rocks, which have δ⁵⁶Fe=0.00±0.05‰, as well as the majority of modern loess, aerosols, riverine loads, marine sediments, and Proterozoic shales. The Fe isotope compositions of hematite, magnetite, Fe carbonate, and pyrite measured in BIFs appears to reflect a combination of (1) mineral-specific equilibrium isotope fractionation, (2) variations in the isotope compositions of the fluids from which they were precipitated, and (3) the effects of metabolic processing of Fe by bacteria. For minerals that may have been in isotopic equilibrium during initial precipitation or early diagenesis, the relative order of δ⁵⁶Fe values appears to decrease in the order magnetite > siderite > ankerite, similar to that estimated from spectroscopic data, although the measured isotopic differences are much smaller than those predicted at low temperature. In combination with on-going experimental determinations of equilibrium Fe isotope fractionation factors, the data for BIF minerals place additional constraints on the equilibrium Fe isotope fractionation factors for the system Fe(III)–Fe(II)–hematite–magnetite–Fe carbonate. δ⁵⁶Fe values for pyrite are the lowest yet measured for natural minerals, and stand in marked contrast to the high δ⁵⁶Fe values that are predicted from spectroscopic data. Some samples contain hematite and magnetite and have positive δ⁵⁶Fe values; these seem best explained through production of high ⁵⁶Fe/⁵⁴Fe reservoirs by photosynthetic Fe oxidation. It is not yet clear if the low δ⁵⁶Fe values measured for some oxides, as well as Fe carbonates, reflect biologic processes, or inorganic precipitation from low-δ⁵⁶Fe ferrous-Fe-rich fluids. However, the present results demonstrate the great potential for Fe isotopes in tracing the geochemical cycling of Fe, and highlight the need for an extensive experimental program for determining equilibrium Fe isotope fractionation factors for minerals and fluids that are pertinent to sedimentary environments.     

Iron and lithium isotope systematics of the Hekla volcano,Iceland — Evidence for Fe isotope fractionation during magma differentiation

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 δ^56/54Fe_IRMM-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 Δ^56/54Fe_M–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 δ^56/54Fe_IRMM-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.     

绿松石低温生长过程中Cu同位素特征及其对产地溯源的意义

绿松石（CuAl₆（PO₄）₄（OH）₈·4（H₂O））是重要的表生宝石矿物,已有研究采用绿松石主量元素Cu的同位素进行产地溯源,但是溯源机理不明确.此外,绿松石生长过程复杂,该过程是否造成Cu同位素组成的显著变化还不甚清楚,这限制了其产地溯源的应用.湖北省竹山县是全球最大的宝石级绿松石产出地,采用MC-ICP-MS对竹山县条带状绿松石的生长条带进行高精度Cu同位素测试.结果表明:绿松石δ65Cu值较高,然而不同条带没有明显变化（δ65Cu=10.99‰~11.54‰）.绿松石含矿热液沉淀过程分馏有限（< 1‰）,这指示绿松石Cu同位素显著变化主要发生在含矿热液的形成过程.原生硫化物的δ65Cu=0±1‰,显著低于绿松石样品测定值,推测引起含矿热液Cu同位素显著分馏的主要原因是原生硫化物发生氧化作用.全球典型绿松石矿区的数据整体与该结果一致,表明绿松石Cu同位素组成主要受源区环境的控制;同一矿区中形成的绿松石,即使经历周期生长产生条带状结构,其Cu同位素组成基本一致.该研究深入探究了Cu同位素示踪绿松石矿区的机理,同时也加深了对低温过程Cu同位素分馏的认识.      

Influence of pH and dissolved Si on Fe isotope fractionation during dissimilatory microbial reduction of hematite

Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low ⁵⁶Fe/⁵⁴Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ⁵⁶Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ⁵⁶Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.     

高温下非传统稳定同位素分馏

过去十几年来,非传统稳定同位素地球化学在高温地质过程的研究中取得了的重大进展。多接收诱导耦合等离子质谱(MC-ICP-MS)的应用引发了稳定同位素分析方法的重大突破,使得精确测定重元素的同位素比值成为可能。本文总结了以Li、Fe和Mg同位素为代表的非传统稳定同位素在岩石地球化学研究中的应用。Li同位素目前被广泛地用于地幔地球化学、俯冲带物质再循环和变质作用的研究中,可以用来示踪岩浆的源区性质和扩散等动力学过程。不同价态的Fe在矿物熔体相之间的分配可以产生Fe同位素分馏,可以发生在地幔交代、部分熔融、分离结晶等过程中。岩浆岩的Mg同位素则大致反映其源区的特征,地幔的Mg同位素组成比较均一,这为研究低温地球化学过程中Mg同位素的分馏提供一个均一的背景。此外,Cl,Si,Cu,Ca,U等等同位素体系也具有广阔的应用前景。对同位素分馏机制的实验研究和理论模拟为理解非传统稳定同位素数据提供了必要的指导。实验表明,高温下具有不同的迁移速度的轻、重同位素可以产生显著的动力学同位素分馏,这一分馏可以在化学扩散、蒸发和凝华等过程中发生;同位素在矿物和熔体以及流体相中化学环境的差异使得不同相之间可以发生平衡分馏。而最近的硅酸盐岩浆的热扩散和热迁移实验则揭示了一种"新"的岩浆分异和同位素分馏机制。沿着温度梯度,硅酸盐岩浆可以发生显著的元素和同位素分异,湿的安山岩可以通过这种方式演变成花岗质成分,因此这个过程可能对陆壳的产生和演化有重大影响。如果温度梯度在岩浆作用中能长期存在,热扩散就可以产生稳定同位素的分馏,这一机制有别于传统的平衡和动力学同位素分馏。 而多个稳定同位素体系的正相关关系是示踪热迁移过程的最有力证据。在热扩散过程中,流体承载的物质的浓度和它的索瑞系数有关。但是这个系数对体系的很多参数非常敏感,变化极大,因此对热扩散效应的研究产生极大的困难。对热扩散实验的镁、钙和铁同位素测量表明,同位素比值的变化与体系的化学组成以及总温度无关,只和温度变化的幅度有关,这意味着即使元素的索瑞系数变化多端,某一元素的同位素之间的索瑞系数的差别总为常数。这一发现有助于简化对热扩散和索瑞系数这一基础物理问题的研究 。     

Links between Mesozoic intermediate–felsic igneous rocks and lower crustal granulite xenoliths,North China Craton: O and Pb isotopic evidence

We present and compare whole-rock and zircon O and Pb isotopic compositions for the Hannuoba granulite xenoliths and Mesozoic intermediate-to-felsic igneous rocks from the Zhangjiakou region, northern margin of the North China Craton, northeast China. The xenoliths have an overall Pb isotopic range similar to rocks from the regionally exposed Neoarchaean granulite terrain. Mesozoic zircons from different types of granulite xenoliths have a narrow range of δ¹⁸O values (6.0–7.7‰) higher than normal mantle δ¹⁸O values (～5.7‰). Mesozoic intermediate–felsic igneous rocks have O and Pb isotopic compositions indistinguishable from the Hannuoba intermediate–mafic granulite xenoliths. Our new data suggest that the Mesozoic igneous rocks and granulite xenoliths are genetically linked and that both were derived from the late Neoarchaean lower crust. This argues against previous proposals that the granulite xenoliths are either products of Mesozoic basaltic underplating or formed by mixing between mantle-derived and pre-existing crustal magmas.