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1.
Copper isotope fractionation in acid mine drainage   总被引：4，自引：0，他引：4  
We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ65Cu values (based on 65Cu/63Cu) of enargite (δ65Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ65Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ65Cu < 1‰). These mineral samples show lower δ65Cu values than stream waters (1.38‰ ? δ65Cu ? 1.69‰). The average isotopic fractionation (Δaq-min = δ65Cuaq − δ65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δaq-mino=-0.57±0.14‰, where mino refers to the starting mineral) and no apparent fractionation for enargite (Δaq-mino=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.  相似文献   

2.
We examined the copper isotope ratio of primary high temperature Cu-sulfides, secondary low temperature Cu-sulfides (and Cu-oxides) as well as Fe-oxides in the leach cap, which represent the weathered remains of a spectrum of Cu mineralization, from nine porphyry copper deposits. Copper isotope ratios are reported as δ65Cu‰ = ((65Cu/63Cusample/65Cu/63CuNIST 976 standard) − 1) ? 103. Errors for all the analyses are ± 0.14‰ (determined by multiple analyses of the samples) and mass bias was corrected through standard-sample-standard bracketing. The overall isotopic variability measured in these samples range from − 16.96‰ to 9.98‰.  相似文献   

3.
The stable copper isotope composition of 79 samples of primary and secondary copper minerals from hydrothermal veins in the Schwarzwald mining district, South Germany, shows a wide variation in δ65Cu ranging from −2.92 to 2.41‰. We investigated primary chalcopyrite, various kinds of fahlores and emplectite, as well as supergene native copper, malachite, azurite, cuprite, tenorite, olivenite, pseudomalachite and chrysocolla. Fresh primary Cu(I) ores have at most localities copper isotope ratios (δ65Cu values) of 0 ± 0.5‰ despite the fact that the samples come from mineralogically different types of deposits covering an area of about 100 by 50 km and that they formed during three different mineralization events spanning the last 300 Ma. Relics of the primary ores in oxidized samples (i.e., chalcopyrite relics in an iron oxide matrix with an outer malachite coating) display low isotope ratios down to −2.92‰. Secondary Cu(I) minerals such as cuprite have high δ65Cu values between 0.4 and 1.65‰, whereas secondary Cu(II) minerals such as malachite show a range of values between −1.55 and 2.41‰, but typically have values above +0.5‰. Within single samples, supergene oxidation of fresh chalcopyrite with a δ value of 0‰ causes significant fractionation on the scale of a centimetre between malachite (up to 1.49‰) and relict chalcopyrite (down to −2.92‰). The results show that—with only two notable exceptions—high-temperature hydrothermal processes did not lead to significant and correlatable variations in copper isotope ratios within a large mining district mineralized over a long period of time. Conversely, low-temperature redox processes seriously affect the copper isotope compositions of hydrothermal copper ores. While details of the redox processes are not yet understood, we interpret the range in compositions found in both primary Cu(I) and secondary Cu(II) minerals as a result of two competing controls on the isotope fractionation process: within-fluid control, i.e., the fractionation during the redox process among dissolved species, and fluid-solid control, i.e., fractionation during precipitation involving reactions between dissolved Cu species and minerals. Additionally, Rayleigh fractionation in a closed system may be responsible for some of the spread in isotope compositions. Our study indicates that copper isotope variations may be used to decipher details of natural redox processes and therefore may have some bearing on exploration, evaluation and exploitation of copper deposits. On the other hand, copper isotope analyses of single archeological artefacts or geological or biological objects cannot be easily used as reliable fingerprint for the source of copper, because the variation caused by redox processes within a single deposit is usually much larger than the inter-deposit variation.  相似文献   

4.
A significant proportion of the copper in the Ca?ariaco Norte porphyry copper deposit in northern Peru occurs in chalcocite and covellite-rich veins and disseminations that exist from the surface to depths greater than 1?km. The overall range of Cu isotopic ratios of 42 mineral separates from Ca?ariaco varies from ?8.42 to 0.61?‰, with near-surface chalcocite and Fe oxides having isotopically depleted values compared to chalcocite, covellite, and chalcopyrite from deeper levels. The majority (34 of 36) of measured Cu sulfides have a typical hypogene copper isotope composition of δ65Cu?=?0.18?±?0.38?‰, with no enriched isotopic signature existing in the Ca?ariaco Norte sulfide data. Thus, the copper isotope data indicate that most of the chalcocite and covellite formed from high-temperature hypogene mineralization processes and that only a minor portion of the deposit is enriched by supergene processes. The nonexistence of an enriched δ65Cu reservoir suggest the presence of an undiscovered lateral/exotic Cu occurrence that enriched 65Cu that remained in solution during weathering. Regardless of the cause, the comparative analysis of the Cu isotope dataset reveals that little exploration potential for an extensive supergene enrichment blanket exists because the weathering history at Ca?ariaco Norte was not conducive to preservation of enriched Cu at depth beneath the leach cap.  相似文献   

5.
Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution-solid = δ65Cusolution − δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to −0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution-solid ranging from ∼+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable.  相似文献   

6.
Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ65Cu, δ66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g−1 Cu and 2084 μg g−1 Zn in the organic horizons. The δ65Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ66ZnIRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.  相似文献   

7.
Copper stable isotope ratios are fractionated during various biogeochemical processes and may trace the fate of Cu during long-term pedogenetic processes. We assessed the effects of oxic weathering (formation of Cambisols) and podzolization on Cu isotope ratios (δ65Cu). Two Cambisols (oxic weathered soils without strong vertical translocations of soil constituents) and two Podzols (soils showing vertical translocation of organic matter, Fe and Al) were analyzed for Cu concentrations, partitioning of Cu in seven fractions of a sequential extraction and δ65Cu values in bulk soil. Cu concentrations in the studied soils were low (1.4-27.6 μg g−1) and Cu was mainly associated with strongly bound Fe oxide- and silicate-associated forms. Bulk δ65Cu values varied between −0.57‰ and 0.44‰ in all studied horizons. The O horizons had on average significantly lighter Cu isotope compositions (−0.21‰) than the A horizons (0.13‰) which can either be explained by Cu isotope fractionation during cycling through the plants or deposition of isotopically light Cu from the atmosphere. Oxic weathering without pronounced podzolization in both Cambisols and a weakly developed Podzol (Haplic Podzol 2) caused no significant isotope fractionation in the single profiles, while a slight tendency to lower δ65Cu values with depth was visible in all four profiles. This is the opposite depth distribution of δ65Cu values to that we observed in hydromorphic soils (soils which show indication of redox changes because of the influence of water saturation) in a previous study. In a more pronounced Podzol (Haplic Podzol 1), δ65Cu values and Cu concentrations decreased from Ah to E horizons and increased again deeper in the soil. Humus-rich sections of the Bhs horizon had higher Cu concentrations (2.8 μg g−1) and a higher δ65Cu value (−0.18‰) than oxide-rich sections (1.9 μg g−1, −0.35‰) suggesting Cu translocation between E and B horizons as organo-Cu complexes. The different depth distributions in oxic weathered and hydromorphic soils and the pronounced vertical differences in δ65Cu values in Haplic Podzol 1 indicate a promising potential of δ65Cu values to improve our knowledge of the fate of Cu during long-term pedogenetic processes.  相似文献   

8.
Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ∼−0.4‰ (−0.25 ± 0.36‰, 1σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.  相似文献   

9.
This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria (Rhodobacter sp.), cyanobacteria (Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria (P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ65Cu (solid-solution) = −1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively.Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution.Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.  相似文献   

10.
We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ56Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ26Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ56Fe; ±0.10‰ for δ26Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ56Feol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ56Feol-opx = −0.05 ± 0.11‰; Δ26Mgol-opx = −0.09 ± 0.12‰; Δ26Mgol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ56Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ26Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ56Fe and δ26Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ56Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ56Fe, the larger deviations from average δ56Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ56Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ56Fe and slightly heavy δ26Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.  相似文献   

11.
The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ7Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ7Li and the clay content of shales (as measured by Al2O3/SiO2), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ7Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ7Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ7Li of −5‰ to + 5‰), with an average (δ7Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ7Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al2O3, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.  相似文献   

12.
We measured Ca stable isotope ratios (δ44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m−2) is present as sulfates (2.5 kmol m−2), and to a lesser extent carbonates (0.4 kmol m−2). In aqueous extracts of variably hydrated calcium sulfate minerals, δ44/40CaE values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ44/40Ca in the top six horizons resembles that of sulfate-δ44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ44/40Ca values observed on Earth. Linear correlation among δ44/40Ca, δ34S and δ18O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ34S values are positively correlated with sulfate-δ18O values (R2 = 0.78) and negatively correlated with sulfate δ44/40CaE values (R2 = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ44/40Ca fractionation factor of −0.4‰ in CaSO4. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.  相似文献   

13.
Eight DSDP/ODP cores were analyzed for major ion concentrations and δ37Cl values of water-soluble chloride (δ37ClWSC) and structurally bound chloride (δ37ClSBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (XWSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (XSBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl− site and the water-soluble Cl− site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ37Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ37Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ37Cl values also have variable Cl− / SO42 ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.  相似文献   

14.
High-precision Zn isotopic variations are reported for carbonaceous chondrites (CC), equilibrated (EOC) and unequilibrated (UOC) ordinary chondrites, iron meteorites from the IAB-IIICD (nonmagmatic) and IIIA (magmatic) groups, and metal from the Brenham pallasite. For irons, δ65Cu values are also reported. Data have also been obtained on a coarse-grained type-B calcium-, aluminum-rich refractory inclusion (CAI) from Allende and on acid leaches of Allende (CV3), Krymka (LL3), and Charsonville (H6). Variations expressed as δ66Zn (deviation in parts per thousand of 66Zn/64Zn in samples relative to a standard) spread over a range of 0.3‰ for carbonaceous chondrites, 2‰ for ordinary chondrites, and 4‰ for irons.The measured 66Zn/64Zn, 67Zn/64Zn, and 68Zn/64Zn ratios vary linearly with mass difference and define a common isotope fractionation line with terrestrial samples, which demonstrates that Zn was derived from an initially single homogeneous reservoir. The δ66Zn values are correlated with meteorite compositions and slightly decrease in the order CI, CM, CV-CO, and to UOC. The isotopically light Zn of Allende CAI and the acid-resistant residues of Allende and Krymka show that the light component is associated with refractory material, presumably minerals from the spinel-group. This, together with the reverse correlation between relative abundances of light Zn isotopes and volatile element abundances, suggests that Zn depletion in planetary bodies with respect to CI cannot be ascribed to devolatilization of CI-like material. These observations rather suggest that refractory material reacted with a gas phase enriched in the lighter Zn isotopes. Alternatively, chondrules with their associated rims should carry a light Zn isotopic signature. The δ66Zn values of unequilibrated chondrites are rather uniform, whereas equilibrated chondrites show distinctly more isotopic variability.The values of δ65Cu-δ66Zn in irons define two trends. The moderate and positively correlated Cu and Zn isotope variations in IIIA and pallasite samples probably reflect crystallization of silicate, sulfide, and solid metal from the liquid metal. The range of δ66Zn values of the IAB-IIICD group is large (>3‰) and contrasts with the moderate fractionation of Cu isotopes. We interpret this feature and the negative δ66Zn-δ65Cu correlation as reflecting mixing, possibly achieved by percolation, between metals from a regolith devolatilized at low temperature (enriched in heavy zinc) and metallic liquids formed within the parent body.  相似文献   

15.
The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al2O3), goethite (α-FeOOH), quartz (α-SiO2), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)sorb-Fe(II)aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ56/54Fe(II)aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)aq to be affected by sorption.  相似文献   

16.
The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ26Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnαMg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnαMg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.  相似文献   

17.
We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ25Mg = −0.14 ± 0.06; δ26Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ7Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ7Li = 3.5 ± 0.5‰, δ25Mg = −0.10 ± 0.03‰ and δ26Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ7Li and δ26Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ7Li and δ26Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ7Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ7Li seen in some oceanic basalts.  相似文献   

18.
Isotopic fractionation of Cu in tektites   总被引：1，自引：0，他引：1  
Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ65Cu < 6.99) in comparison to the terrestrial crust (δ65Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ65Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ65Cu ≈ 0).An increase of δ65Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn2+ vs. Cu+), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.  相似文献   

19.
Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe2O4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ66Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献   

20.
Morphologies, petrographic settings and carbon and nitrogen isotopic compositions of graphites in the Acapulco meteorite, the latter determined by secondary ionization mass spectrometry, are reported. Seven different graphite morphologies were recognized, the majority of which occur enclosed exclusively in kamacite. Individual graphite grains also rarely occur in the silicate matrix. Kamacite rims surrounding taenite cores of metal grains are separated from the Ni-rich metal cores by graphite veneers. These graphite veneers impeded or prevented Ni-Fe interdiffusion during cooling. In addition, matrix FeNi metal contains considerable amounts of phosphorous (≈ 700 ppm) and silicon (≈ 300 ppm) (Pack et al., 2005 in preparation) thus indicating that results of laboratory cooling experiments in the Fe-Ni binary system are inapplicable to Acapulco metals. Graphites of different morphologies display a range of carbon and nitrogen isotopic compositions, indicating a diversity of source regions before accretion in the Acapulco parent body. The isotopic compositions point to at least three isotopic reservoirs from which the graphites originated: (1) A reservoir with heavy carbon, represented by graphite in silicates (δ13C = 14.3 ± 2.4 ‰ and δ15N = −103.4 ± 10.9 ‰), (2) A reservoir with isotopically light carbon and nitrogen, characteristic for the metals. Its C- and N-isotopic compositions are probably preserved in the graphite exsolutions that are isotopically light in carbon and lightest in nitrogen (δ13C = −17 to −23 ‰ δ15N = −141 to −159 ‰). (3) A reservoir with an assumed isotopic composition (δ13C ∼ −5 ‰; δ15N ∼ −50 ‰). A detailed three-dimensional tomography in reflected light microscopy of the decorations of metal-troilite spherules in the cores of orthopyroxenes and olivines and metal-troilite veins was conducted to clarify their origin. Metal and troilite veins are present only near the fusion crust. Hence, these veins are not pristine to Acapulco parent body but resulted during passage of Acapulco in Earth’s atmosphere. A thorough search for symplectite-type silicate-troilite liquid quench textures was conducted to determine the extent of closed-system partial silicate melting in Acapulco.Metal-troilite spherules in orthopyroxenes and olivines are not randomly distributed but decorate ferromagnesian silicate restite cores, indicating that the metal-spherule decoration around restite silicates took place in a silicate partial melt. Graphite inclusions in these spherules have C- and N- isotopic compositions (δ13C = −2.9 ± 2.5 ‰ and δ15N = −101.2 ± 32 ‰) close to the average values of graphite in metals and in the silicate matrix, thus strongly suggesting that they originated from a mixture of graphite inclusions in metals and silicate matrix graphite during a closed system crystallization process subsequent to silicate-metal-sulfide partial melting. Troilite-orthopyroxene quench symplectite textures in orthopyroxene rims are clear evidence that silicate-sulfide partial melting took place in Acapulco. Due to petrographic heterogeneity on a centimeter scale, bulk REE abundances of individual samples or of individual minerals provide only limited information and the REE abundances alone are not entirely adequate to unravel the formational processes that prevailed in the acapulcoite-lodranite parent body. The present investigations demonstrate the complexity of the evolutionary stages of acapulcoites from accretion to parent body processes.  相似文献   

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