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1.
Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ56Fesolution-hornblende for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of 56Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ56Fesolution-starting material = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.  相似文献   

2.
Various metacarbonate and associated calc-silicate rocks form minor but genetically significant components of the lithological units in the Bohemian Massif of the Variscan orogen in Central Europe.These rocks vary in terms of their lithostratigraphy,chemical composition and mineral assemblage(dolomite/calcite ratio,silicate abundance).Tourmaline is present in five paragenetic settings within the metacarbonate and calc-silicate units.TypeⅠcomprises individual,euhedral,prismatic grains and grain aggregates in a carbonate-dominant(calcite±dolomite)matrix poor in silicates.TypeⅡis characterized by euhedral to subhedral grains and coarse-to fine-grained aggregates in silicate-rich layers/nests within metacarbonate bodies whereas typeⅢoccurs as prismatic grains and aggregates at the contact zones between carbonate and associated silicate host rocks.TypeⅣis in veins crosscutting metacarbonate bodies,and typeⅣtourmaline occurs at the exocontacts of elbaite-subtype granitic pegmatite.Tourmaline from the different settings shows distinctive compositional features.Typical for typeⅠare Mg-rich compositions,with fluor-uvite>dravite>>magnesio-lucchesiite.Tourmalines from typeⅡsilicate-rich layers/nests are highly variable,corresponding to oxy-schorl,magnesio-foitite,Al-rich dravite and fluor-uvite.Typical for typeⅢtourmalines are Ca,Ti-bearing oxy-dravite compositions.The typeⅣveins feature dravite and fluor-uvite tourmaline compositions whereas typeⅤtourmaline is Li,F-rich dravite.Tourmaline is the only Bbearing phase in paragenetic typesⅠ-Ⅳ,where it is characterised by two principal ranges of B-isotope composition(δ^11B=-13‰to-9‰and-18‰to-14‰).These ranges correspond to regionally different units of the Moldanubian Zone.Thus,the Svratka Unit(Moldanubian Zone s.l.)contains only isotopically lighter tourmaline(δ^11B=-18‰to-14‰),whereas metacarbonates in the Poli?ka unit(Teplá-Barrandian Zone)and Olesnice unit(Moravicum of the Moravo-Silesian Zone)has exclusively isotopically heavier tourmaline(δ^11B=-9‰to-13‰).Tourmalines from metacarbonates in the Variegated Unit cover both ranges of isotope composition.The isotopically light end of the B isotope range may indicate the presence of continental evaporites within individual investigated areas.On the other hand,variations in the range of~8δ-units is consistent with the reported shift in B isotopic composition of metasedimentary rocks of the Bohemian Massif due to the prograde metamorphism from very-low grade to eclogite facies.In contrast to the metacarbonate-hosted settings,tourmaline of paragenetic type V from the exocontact of granitic pegmatites displays a significantly heavier range ofδ^11B(as low as-7.7‰to-0.6‰),which is attributed to partitioning of 10 B to cogenetic axinite and/or different B-signature of the source pegmatite containing tourmaline with heavyδ^11B signature.  相似文献   

3.
Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42− and Cl− salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor αFe(III)aq-Fe(II)aq ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9‰ (αFe(III)aq-Fe(II)aq ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.  相似文献   

4.
This work presents isotopic data for the non-traditional isotope systems Fe, Cu, and Zn on a set of Chicxulub impactites and target lithologies with the aim of better documenting the dynamic processes taking place during hypervelocity impact events, as well as those affecting impact structures during the post-impact phase. The focus lies on material from the recent IODP-ICDP Expedition 364 Hole M0077A drill core obtained from the offshore Chicxulub peak ring. Two ejecta blanket samples from the UNAM 5 and 7 cores were used to compare the crater lithologies with those outside of the impact structure. The datasets of bulk Fe, Cu, and Zn isotope ratios are coupled with petrographic observations and bulk major and trace element compositions to disentangle equilibrium isotope fractionation effects from kinetic processes. The observed Fe and Cu isotopic signatures, with δ56/54Fe ranging from ?0.95‰ to 0.58‰ and δ65/63Cu from ?0.73‰ to 0.14‰, mostly reflect felsic, mafic, and carbonate target lithology mixing and secondary sulfide mineral formation, the latter associated to the extensive and long-lived (>105 years) hydrothermal system within Chicxulub structure. On the other hand, the stable Zn isotope ratios provide evidence for volatility-governed isotopic fractionation. The heavier Zn isotopic compositions observed for the uppermost part of the impactite sequence and a metamorphic clast (δ66/64Zn of up to 0.80‰ and 0.87‰, respectively) relative to most basement lithologies and impact melt rock units indicate partial vaporization of Zn, comparable to what has been observed for Cretaceous-Paleogene boundary layer sediments around the world, as well as for tektites from various strewn fields. In contrast to previous work, our data indicate that an isotopically light Zn reservoir (δ66/64Zn down to ?0.49‰), of which the existence has previously been suggested based on mass balance considerations, may reside within the upper impact melt rock (UIM) unit. This observation is restricted to a few UIM samples only and cannot be extended to other target or impact melt rock units. Light isotopic signatures of moderately volatile elements in tektites and microtektites have previously been linked to (back-)condensation under distinct kinetic regimes. Although some of the signatures observed may have been partially overprinted during post-impact processes, our bulk data confirm impact volatilization and condensation of Zn, which may be even more pronounced at the microscale, with variable degrees of mixing between isotopically distinct reservoirs, not only at proximal to distal ejecta sites, but also within the lithologies associated with the Chicxulub impact crater.  相似文献   

5.
Photoautotrophic bacteria that oxidize ferrous iron (Fe[II]) under anaerobic conditions are thought to be ancient in origin, and the ferric (hydr)oxide mineral products of their metabolism are likely to be preserved in ancient rocks. Here, two enrichment cultures of Fe(II)-oxidizing photoautotrophs and a culture of the genus Thiodictyon were studied with respect to their ability to fractionate Fe isotopes. Fe isotope fractionations produced by both the enrichment cultures and the Thiodictyon culture were relatively constant at early stages of the reaction progress, where the 56Fe/54Fe ratios of poorly crystalline hydrous ferric oxide (HFO) metabolic products were enriched in the heavier isotope relative to aqueous ferrous iron (Fe[II]aq) by ∼1.5 ± 0.2‰. This fractionation appears to be independent of the rate of photoautotrophic Fe(II)-oxidation, and is comparable to that observed for Fe isotope fractionation by dissimilatory Fe(III)-reducing bacteria. Although there remain a number of uncertainties regarding how the overall measured isotopic fractionation is produced, the most likely mechanisms include (1) an equilibrium effect produced by biological ligands, or (2) a kinetic effect produced by precipitation of HFO overlaid upon equilibrium exchange between Fe(II) and Fe(III) species. The fractionation we observe is similar in direction to that measured for abiotic oxidation of Fe(II)aq by molecular oxygen. This suggests that the use of Fe isotopes to identify phototrophic Fe(II)-oxidation in the rock record may only be possible during time periods in Earth’s history when independent evidence exists for low ambient oxygen contents.  相似文献   

6.
《Chemical Geology》2007,236(3-4):181-198
Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of 97Mo/95Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ97Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ97Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O2 conditions in the bottom water through the Holocene indicates that increased O2 concentrations are generally associated with low δ97Mo/95Mo values of the sediments, whereas lowered O2 contents of the bottom water are accompanied by relatively high δ97Mo/95Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.  相似文献   

7.
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   

8.
This study explores the fractionation of iron isotopes (57Fe/54Fe) in an organic-rich mudstone succession, focusing on core and outcrop material sampled from the Upper Jurassic Kimmeridge Clay Formation type locality in south Dorset, UK. The organic-rich environments recorded by the succession provide an excellent setting for an investigation of the mechanisms by which iron isotopes are partitioned among mineral phases during biogeochemical sedimentary processes.Two main types of iron-bearing assemblage are defined in the core material: mudstones with calcite ± pyrite ± siderite mineralogy, and ferroan dolomite (dolostone) bands. A cyclic data distribution is apparent, which reflects variations in isotopic composition from a lower range of δ57Fe values associated with the pyrite/siderite mudstone samples to the generally higher values of the adjacent dolostone samples. Most pyrite/siderite mudstones vary between −0.4 and 0.1‰ while dolostones range between −0.1 and 0.5‰, although in very organic-rich shale samples below 360 m core depth higher δ57Fe values are noted. Pyrite nodules and pyritized ammonites from the type exposure yield δ57Fe values of −0.3 to −0.45‰. A fractionation model consistent with the δ57Fe variations relates the lower δ57Fe pyrite and siderite ± pyrite mudstones values to the production of isotopically depleted Fe(II) during biogenic reduction of the isotopically heavier lithogenic Fe(III) oxides. A consequence of this reductive dissolution is that a 57Fe-enriched iron species must be produced that potentially becomes available for the formation of the higher δ57Fe dolostones. An isotopic profile across a dolostone band reveals distinct zonal variations in δ57Fe, characterized by two peaks, respectively located above and below the central part of the band, and decoupling of the isotopic composition from the iron content. This form of isotopic zoning is shown to be consistent with a one-dimensional model of diffusional-chromatographic Fe-isotope exchange between dolomite and isotopically enriched pore water. An alternative mechanism envisages the infiltration of dissolved ferrous iron from variable (high and low) δ57Fe sources during coprecipitation of Fe(II) ion with dolomite. The study provides clear evidence that iron isotopes are cycled during the formation and diagenesis of organic carbon-rich sediments.  相似文献   

9.
Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)aq - oxide interaction will produce low δ56Fe values for Fe(II)aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ56Fe Fe(II)aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ56Fe aqueous Fe(II) in many natural systems.  相似文献   

10.
The isotopic composition of dissolved Cu and solid Cu-rich minerals [δ65Cu (‰) = (65Cu/63Cusample/65Cu/63Custd) - 1)*1000] were monitored in batch oxidative dissolution experiments with and without Thiobacillus ferrooxidans. Aqueous copper in leach fluids released during abiotic oxidation of both chalcocite and chalcopyrite was isotopically heavier (δ65Cu = 5.34‰ and δ65Cu = 1.90‰, respectively, [±0.16 at 2σ]) than the initial starting material (δ65Cu = 2.60 ± 0.16‰ and δ65Cu = 0.58 ± 0.16‰, respectively). Isotopic mass balance between the starting material, aqueous copper, and secondary minerals precipitated in these experiments explains the heavier isotopic values of aqueous copper. In contrast, aqueous copper from leached chalcocite and chalcopyrite inoculated with Thiobacillus ferrooxidans was isotopically similar to the starting material. The lack of fractionation of the aqueous copper in the biotic experiments can best be explained by assuming a sink for isotopically heavy copper present in the bacteria cells with δ65Cu = 5.59 ± 0.16‰. Consistent with this inference, amorphous Cu-Fe oxide minerals are observed surrounding cell membranes of Thiobacillus grown in the presence of dissolved Cu and Fe.Extrapolating these experiments to natural supergene environments implies that release of isotopically heavy aqueous Cu from oxidative leach caps, especially under abiotic conditions, should result in precipitates in underlying enrichment blankets that are isotopically heavy. Where iron-oxidizing cells are involved, isotopically heavy oxidized Cu entrained in cellular material may become associated with leach caps, causing the released aqueous Cu to be less isotopically enriched in the heavy isotope than predicted for the abiotic system. Rayleigh fractionation trends with fractionation factors calculated from our experiments for both biotic and abiotic conditions are consistent with large numbers of individual abiotic or biotic leaching events, explaining the supergene chalcocites in the Morenci and Silver Bell porphyry copper deposits.  相似文献   

11.
Magnesium isotopic compositions, along with new Sr–Nd–Pb isotopic data and elemental analyses, are reported for 12 Miocene tourmaline-bearing leucogranites, 15 Eocene two-mica granites and 40 metamorphic rocks to investigate magnesium isotopic behaviors during metamorphic processes and associated magmatism and constrain the tectonic-magmatic-metamorphic evolution of the Himalayan orogeny. The gneisses, granulites and amphibolites represent samples of the Indian lower crust and display large range in δ26Mg from −0.44‰ to −0.09‰ in mafic granulites, −0.44‰ to −0.10‰ in amphibolites, and −0.70‰ to −0.03‰ in granitic gneisses. The average Mg isotopic compositions of the granitic gneisses (−0.19 ± 0.34‰), mafic granulites (−0.22 ± 0.17‰) and amphibolites (−0.25 ± 0.24‰) are similar, indicating the limited Mg isotope fractionation during prograde metamorphism from granitic gneisses to mafic granulites and retrograde metamorphism from mafic granulites to amphibolites. The Eocene two-mica granites and Miocene leucogranites are characterized by large variations in elemental and Sr–Nd–Pb isotopic compositions. The leucogranites and two-mica granites have their corresponding (87Sr/86Sr)i varying from 0.7282 to 0.7860 and 0.7163 to 0.7191, (143Nd/144Nd)i from 0.511888 to 0.512040 and 0.511953 to 0.512076, 207Pb/204Pb from 15.7215 to 15.7891 and 15.7031 to 15.7317, 208Pb/204Pb from 38.8521 to 39.5286 and 39.2710 to 39.4035, and 206Pb/204Pb from 18.4748 to 19.0139 and 18.7834 to 18.9339. However, they have similar Mg isotopic compositions (−0.21‰ to +0.06‰ versus −0.24‰ to +0.09‰), which did not originate from fractional crystallization nor source heterogeneity. Based on hornblende/biotite/muscovite dehydration melting reaction and Mg isotopic variations in two-mica granites and leucogranites with the proceeding metamorphism, along with elemental discrimination diagrams, Eocene two-mica granites and Miocene leucogranites could be related to hornblende dehydration melting and muscovite dehydration melting, respectively. Mg isotopic compositions of Eocene two-mica granites become heavier compared to the source because of residues of isotopically light garnet in the source; while those of Miocene leucogranites become lighter because of entrainment of isotopically light garnet from the source region. Thus, a new model for crustal anatexis and Himalayan orogenesis was proposed based on the Mg isotope fractionation in the leucogranites and metamorphic rocks. This model emphasizes a successive process from Indian continental subduction to rapid exhumation of the Higher Himalayan Crystalline Series (HHCS). The former underwent high-temperature (HT) and high-pressure (HP) granulite-facies prograde metamorphism, which resulted in the hornblende dehydration melting and the formation of Eocene two-mica granites; while the latter experienced amphibolite-facies retrogression and decompression, which resulted in the muscovite dehydration melting and the formation of Miocene leucogranites.  相似文献   

12.
Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl−) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using 57Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl− (∼10 mM HNO3) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl− solutions.The average measured equilibrium isotope fractionations, ΔFe(III)-Fe(II), in 0, 11, and 111 mM Cl− solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured ΔFe(III)-Fe(II) fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl− solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl− contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl− contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.  相似文献   

13.
Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ56Fe and δ66Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ56Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ66Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ56Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ66Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ56Fe and decreasing δ66Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ56Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ56Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ66Zn values of sphalerite and heavier δ56Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ66Zn values and heavier δ56Fe values of modified samples.  相似文献   

14.
This study presents molecular orbital/density functional theory (MO/DFT) calculations of the electronic structure, vibrational frequencies, and equilibrium isotope fractionation factors for iron desferrioxamine B (Fe-DFO-B) complexes in aqueous solution. In general, there was good agreement between the predicted properties of Fe(III)-DFO-B and previously published experimental and theoretical results. The predicted fractionation factor for equilibrium between Fe(III)-DFO-B and Fe(III)-catecholate at 22 °C, 0.68 ± 0.25‰, was in good agreement with a previously measured isotopic difference between bacterial cells and solution during the bacterial-mediated dissolution of hornblende [Brantley S. L., Liermann L. and Bullen T. D. (2001) Fractionation of Fe isotopes by soil microbes and organic acids. Geology29, 535-538]. Conceptually, this agreement is consistent with the notion that Fe is first removed from mineral surfaces via complexation with small organic acids (e.g., oxalate), subsequently sequestered by DFO-B in solution, and ultimately delivered to bacterial cells by Fe(III)-DFO-B complexes. The ability of DFO-B to discriminate between Fe(III) and Fe(II)/Al(III) was investigated with Natural Bond Orbital (NBO) analysis and geometry calculations of each metal-DFO-B complex. The results indicated that higher affinity for Fe(III) is not strictly a function of bond length but also the degree of Fe-O covalent bonding.  相似文献   

15.
Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3-Fe(II)aq fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.  相似文献   

16.
We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc4Zr3O12), and an unnamed ((Ti,Mg,Sc,Al)3O5) mineral, davisite (CaScAlSiO6), eringaite (Ca3(Sc,Y,Ti)2Si3O12), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)2O3), lakargiite (CaZrO3), warkite (Ca2Sc6Al6O20), panguite ((Ti,Al,Sc,Mg,Zr,Ca)1.8O3), Y-rich perovskite ((Ca,Y)TiO3), tazheranite ((Zr,Ti,Ca)O2−x), thortveitite (Sc2Si2O7), zirconolite (orthorhombic CaZrTi2O7), and zirkelite (cubic CaZrTi2O7). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly 16O-rich (Δ17O ∼ −23‰), except for one CH UR CAI, which is uniformly 16O-depleted (Δ 17O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ17O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)3O5 (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ17O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being 16O-depleted to various degrees relative to uniformly 16O-rich (Δ17O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a 16O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an 16O-depleted gaseous reservoir providing an evidence for large variations in Δ17O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in 16O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)3O5 intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with 16O-depleted reservoirs occurred.  相似文献   

17.
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   

18.
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   

19.
The dramatic decline in aqueous Ni concentrations in the Archean oceans during the Great Oxygenation Event is evident in declining solid phase Ni concentrations in Banded Iron Formations (BIFs) at the time. Several experiments have been performed to identify the main removal mechanisms of Ni from seawater into BIFs, whereby adsorption of Ni onto ferrihydrites has shown to be an efficient process. Ni isotopic measurements have shown limited isotopic fraction during this process, however, most experiments have been conducted in simple solutions containing varying proportions of dissolved Fe and Ni as NO3 salts, as opposed to Cl salts which are dominant in seawater. Further, Archean oceans were, before the advent of siliceous eukaryotes, likely saturated with amorphous Si as seen in the interlayered chert layers within BIFs. Despite Si being shown to greatly affect the Ni elemental partitioning onto ferrihydrite solids, no studies have been made on the effects of Si on the Ni isotope fractionation. Here we report results of multiple coprecipitation experiments where ferrihydrite precipitated in mixed solutions with Ni and Si. Ni concentrations in the experiments ranged between 200 and 4000 nM for fixed concentrations of Si at either 0, 0.67 or 2.2 mM. The results show that Si at these concentrations has a limited effect on the Ni isotope fractionation during coprecipitation of ferrihydrite. At 0.67 mM, the saturation concentration of cristobalite, the isotopic fractionation factors between the precipitating solid and experimental fluid are identical to experiments not containing Si (0.34 ± 0.17‰). At 2.2 mM Si, and the saturation concentration of amorphous silica, however, the Ni isotopic composition of the ferrihydrite solids deviate to more negative values and show a larger variation than at low or no Si, and some samples show fractionation of up to 0.5‰. Despite this seemingly more unstable fractionation behaviour, the combined results indicate that even at as high concentrations of Si as 2.2 mM, the δ60Ni values of the forming ferrihydrites does not change much. The results of our study implicate that Si may not be a major factor in fractionating stable Ni isotopes, which would make it easier to interpret future BIF record and reconstruct Archean ocean chemistry.  相似文献   

20.
The Qiman Tagh W-Sn belt lies in the westernmost section of the East Kunlun Orogen, NW China, and is associated with early Paleozoic monzogranites, tourmaline is present throughout this belt. In this paper we report chemical and boron isotopic compositions of tourmaline from wall rocks, monzogranites, and quartz veins within the belt, for studying the evolution of ore-forming fluids. Tourmaline crystals hosted in the monzogranite and wall rocks belong to the alkali group, while those hosted in quartz veins belong to both the alkali and X-site vacancy groups. Tourmaline in the walk rocks lies within the schorl-dravite series and becomes increasingly schorlitic in the monzogranite and quartz veins. Detrital tourmaline in the wall rocks is commonly both optically and chemically zoned,with cores being enriched in Mg compared with the rims. In the Al-Fe-Mg and Ca-Fe-Mg diagrams,tourmaline from the wall rocks plots in the fields of Al-saturated and Ca-poor metapelite, and extends into the field of Li-poor granites, while those from the monzogranite and quartz veins lie within the field of Li-poor granites. Compositional substitution is best represented by the MgFe_(-1), Al(NaR)_(-1), and AlO(Fe(OH))_(-1) exchange vectors. A wider range of δ~(11)B values from -11.1‰ to -7.1‰ is observed in the wall-rock tourmaline crystals, the B isotopic values combining with elemental diagrams indicate a source of metasediments without marine evaporates for the wall rocks in the Qiman Tagh belt. The δ~(11)B values of monzogranite-hosted tourmaline range from -10.7‰ and-9.2‰, corresponding to the continental crust sediments, and indicate a possible connection between the wall rocks and the monzogranite. The overlap in δ~(11)B values between wall rocks and monzogranite implies that a transfer of δ~(11)B values by anataxis with little isotopic fractionation between tourmaline and melts. Tourmaline crystals from quartz veins have δ~(11)B values between -11.0‰ and-9.6‰, combining with the elemental diagrams and geological features, thus indicating a common granite-derived source for the quartz veins and little B isotopic fractionation occurred. Tourmalinite in the wall rocks was formed by metasomatism by a granite-derived hydrothermal fluid, as confirmed by the compositional and geological features.Therefore, we propose a single B-rich sedimentary source in the Qiman Tagh belt, and little boron isotopic fractionation occurred during systematic fluid evolution from the wall rocks, through monzogranite, to quartz veins and tourmalinite.  相似文献   

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