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1.
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   

2.
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   

3.
Silicon isotopes in meteorites and planetary core formation   总被引：1，自引：0，他引：1  
The silicon (Si) isotope compositions of 42 meteorite and terrestrial samples have been determined using MC-ICPMS with the aim of resolving the current debate over their compositions and the implications for core formation. No systematic δ30Si differences are resolved between chondrites (δ30Si = −0.49 ± 0.15‰, 2σSD) and achondrites (δ30Si = −0.47 ± 0.11‰, 2σSD), although enstatite chondrites are consistently lighter (δ30Si = −0.63 ± 0.07‰, 2σSD) in comparison to other meteorite groups. The data reported here for meteorites and terrestrial samples display an average difference Δ30SiBSE−meteorite∗ = 0.15 ± 0.10‰, which is consistent within uncertainty with previous studies. No effect from sample heterogeneity, preparation, chemistry or mass spectrometry can be identified as responsible for the reported differences between current datasets. The heavier composition of the bulk silicate Earth is consistent with previous conclusions that Si partitioned into the metal phase during metal-silicate equilibration at the time of core formation. Fixing the temperature of core formation to the peridotite liquidus and using an appropriate metal silicate fractionation factor (ε ∼0.89), the Δ30SiBSE−meteorite∗ value from this study indicates that the Earth core contains at least 2.5 and possibly up to 16.8 wt% Si.  相似文献   

4.
The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ17O = 0.95 * δ18O − 3.24; R2 = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo99.6-99.8; δ18O = −7.2‰ to −5.5‰; δ17O = −9.6‰ to −8.2‰) are more 16O-rich than the isolated olivine grains (Fo39.6-86.8; δ18O = 3.1‰ to 5.1‰; δ17O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo97.2-99.8) with oxygen-isotope compositions (δ18O = −5.2‰ to 5.9‰; δ17O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ17O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with 16O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R2 = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAMslope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with 16O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.  相似文献   

5.
Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ18O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO2, Al2O3). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ56Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ18O and δ56Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ56Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ18O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ18O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ18O and δ56Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).  相似文献   

6.
Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ13Cmean = −2.49 ± 0.99‰; δ18Omean = −9.43 ± 1.40‰). The δ13C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ18O values are typical of fresh water carbonates. Covariation between δ13C and δ18O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ13Cmean = −2.06 ± 0.84‰; δ18Omean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)molar, δ13C and δ18O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.  相似文献   

7.
The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average δ202Hg value of −0.91‰ ± 0.15‰ (n = 5, 1 SD) and Δ199Hg value of 0.11‰ ± 0.03‰ (n = 5, 1 SD). Background sediments have an average δ202Hg of −0.76‰ ± 0.16‰ (n = 5, 1 SD) and Δ199Hg of 0.05‰ ± 0.01‰ (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.  相似文献   

8.
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   

9.
Tissue N contents and δ15N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ15N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ15N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH3 released from excretory wastes and sewage, while the less negative δ15N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH3. With more negative values in the urban area than in the rural area, the pattern of moss δ15N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NOx–N. Therefore, NHx–N is the dominant N form deposited in the Guiyang area, which is supported by higher NHx–N than NOx–N in local atmospheric deposition. From the data showing that moss is responding to NHx–N/NOx–N in deposition it can be further demonstrated that the variation of moss δ15N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NHx/agriculture-NHx than the ratio of NHx–N/NOx–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.  相似文献   

10.
Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (32S/33S/34S/36S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ34S-Δ33S-Δ36S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ34S = −5 ± 2‰; Δ33S = −3 ± 1‰); (2) MD sulfate (δ34S = +10 ± 3‰); (3) non-MD sulfur (δ34S > +6‰; Δ33S > +4‰); and (4) igneous MD sulfur (δ34S = Δ33S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in 34S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO2. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in 34S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ33S/δ34S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ36S values and steep Δ36S/Δ33S slopes, which deviate from the main Archean array (Δ36S/Δ33S = −0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ36S/Δ33S = −5 to −11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested.  相似文献   

11.
Atmospheric carbon dioxide is widely studied using records of CO2 mixing ratio, δ13C and δ18O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally 13C18O16O) provides an additional constraint. In particular, the mass 47 anomaly (Δ47) can distinguish between CO2 produced by high temperature combustion processes vs. low temperature respiratory processes. Δ47 is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured 13C and 18O values. In this study, we estimate the δ13C (vs. VPDB), δ18O (vs. VSMOW), δ47, and Δ47 values of CO2 from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO2 from these sources. δ47 is defined as , where is the R47 value for a hypothetical CO2 whose δ13CVPDB = 0, δ18OVSMOW = 0, and Δ47 = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO2] from 383 to 404 μmol mol−1, in δ13C and δ18O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ47 from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ13C (similar to the δ13C of local gasoline), δ18O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ47 of 0.41 ± 0.03‰. Both δ18O and Δ47 values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO2 and water generated by combustion of gasoline-air mixtures. Samples of CO2 from human breath were found to have δ13C and δ18O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ47 in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.  相似文献   

12.
The equilibrium Mg isotope fractionation factor between epsomite and aqueous MgSO4 solution has been measured using the three isotope method in recrystallization experiments conducted at 7, 20, and 40 °C. Complete or near-complete isotopic exchange was achieved within 14 days in all experiments. The Mg isotope exchange rate between epsomite and MgSO4 solution is dependent on the temperature, epsomite seed crystal grain size, and experimental agitation method. The Mg isotope fractionation factors (Δ26Mgeps-sol) at 7, 20, and 40 °C are 0.63 ± 0.07‰, 0.58 ± 0.16‰, and 0.56 ± 0.03‰, respectively. These values are indistinguishable within error, indicating that the Mg isotope composition of epsomite is relatively insensitive to temperature. The magnitude of the isotope fractionation factor (Δ26Mgeps-sol = ca. 0.6‰ between 7 and 40 °C) indicates that significant Mg isotope variations can be produced in evaporite sequences, and Mg isotopes may therefore, constrain the degree of closed-system behavior, paleo-humidity, and hydrological history of evaporative environments.  相似文献   

13.
Molybdenum (Mo) isotope studies in black shales can provide information about the redox evolution of the Earth’s oceans, provided the isotopic consequences of Mo burial into its major sinks are well understood. Previous applications of the Mo isotope paleo-ocean redox proxy assumed quantitative scavenging of Mo when buried into sulfidic sediments. This paper contains the first complete suite of Mo isotope fractionation observations in a sulfidic water column and sediment system, the meromictic Lake Cadagno, Switzerland, a small alpine lake with a pronounced oxygen-sulfide transition reaching up to H2S ∼ 200 μM in the bottom waters (or about 300 μM total sulfide: ΣS2− = H2S + HS− + S2−). We find that Mo behaves conservatively in the oxic zone and non-conservatively in the sulfidic zone, where dissolved Mo concentrations decrease from 14 nM to 2-8 nM across this transition. Dissolved Mo in the upper oxic waters has a δ98Mooxic = 0.9 ± 0.1‰, which matches that of the riverine input, δ98Moriver = 0.9 ± 0.1‰. In the deeper sulfidic waters, a subaquatic source delivers Mo at 1.55 ± 0.1‰, but the dissolved Mo is even heavier at δ98Mosulfidic = 1.8‰. Sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in Mo with depth, with δ98Mo values significantly fractionated at −0.8‰ to −1.2‰ both near the chemocline and in the deepest trap. Suspended particulates in the sulfidic waters carry lighter Mo than the ambient dissolved Mo pool by ∼0.3-1.5‰. Sedimentary Mo concentrations correlate with total organic carbon and yield Mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area. Solid-phase Mo in the sediment shows a slightly positive δ98Mo trend with depth, from δ98Mo = 1.2‰ to 1.4‰ while the pore waters show dramatic enrichments of Mo (>2000 nM) with a relatively light isotope signature of δ98Mo = 0.9-1.0‰.These data are explained if Mo is converted to particle-reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles. Isotope fractionation is expressed in the water column, despite the high sulfide concentrations, because the rate of Mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation. However, elemental and isotopic mass balances show that Mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water. This efficient Mo drawdown is expected to occur in settings where H2S is very much in excess over Mo or in a restricted setting where the water renewal rate is slow compared to the Mo burial rate. We present a model for the Mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems.  相似文献   

14.
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   

15.
The sources and petrogenetic processes that generated some of the Earth’s oldest continental crust have been more tightly constrained via an integrated, in situ (U-Pb, O and Hf) isotopic approach. The minerals analysed were representative zircon from four Eoarchaean TTG tonalites and two felsic volcanic rocks, and olivine from one harzburgite/dunite of the Itsaq Gneiss Complex (IGC), southern West Greenland. The samples were carefully chosen from localities with least migmatisation, metasomatism and strain. Zircon was thoroughly characterized prior to analysis using cathodoluminescence, scanning electron, reflected and transmitted light imaging. The zircon from all but one sample showed only minor post-magmatic recrystallisation. 207Pb/206Pb dating of oscillatory-zoned zircon using SHRIMP RG (n = 142) indicates derivation of the felsic igneous rocks from different batches of magma at 3.88, 3.85, 3.81, 3.80 and 3.69 Ga.Analyses of 18O/16O compositions of olivine from a harzburgite/dunite (n = 8) using SHRIMP II in multi-collector mode, indicate that the oxygen isotopic composition of this sample of Eoarchaean mantle (δ18OOl = 6.0 ± 0.4‰) was slightly enriched in 18O, but not significantly different from that of the modern mantle. Zircon δ18O measurements from the six felsic rocks (n = 93) record mean or weighted mean compositions ranging from 4.9 ± 0.7‰ to 5.1 ± 0.4‰, with recrystallised domains showing no indication of oxygen isotopic exchange during younger tectonothermal events. δ18OZr compositions indicate that the primary magmas were largely in equilibrium with the mantle or mantle-derived melts generated at similar high temperatures, while calculated tonalite δ18OWR compositions (6.7-6.9‰) resemble those of modern adakites.LA-MC-ICPMS zircon 176Hf/177Hf analyses were obtained from six samples (n = 122). Five samples record weighted mean initial εHf compositions ranging from to 0.5 ± 0.6 to −0.1 ± 0.7 (calculated using λ176Lu = 1.867 × 10−11 yr−1), while one sample records a composition of 1.3 ± 0.7, indicating the magmas were generated from a reservoir with a time averaged, near chondritic Lu/Hf. The derivation of TTG magmas from a chondritic Lu/Hf source implies either that there was not voluminous continental crustal growth nor major mantle differentiation leading to Lu/Hf fractionation during the Hadean or Eoarchaean, or alternatively that rapid recycling of an early formed crust allowed the early mantle to maintain a chondritic Lu/Hf.Previous studies have demonstrated that ancient TTG rocks were mostly produced by dehydration melting of mafic rocks within the stability field of garnet, probably in flatly-subducted or buried oceanic crust. The oxygen isotopic signatures measured here at high spatial resolution allow the source materials to be better defined. Melting of a mixed mafic source consisting of ∼80% unaltered gabbro (δ18OWR = 5.5‰) with ∼20% hydrothermally altered gabbro/basalt (δ18OWR = 4.0‰) would produce tonalite magmas within the average compositional range observed. 18O-enriched components such as altered shallow basaltic oceanic crust and pelagic or continental sediments were not present in the sources of these TTG melts. The absence of high 18O signatures may indicate either the rarity of low temperature altered sediments, or their effective removal from the down-going slab.  相似文献   

16.
Measurements are presented of the magnesium isotopic composition of chlorophyll-a, extracted from cyanobacteria, relative to the isotopic composition of the culture medium in which the cyanobacteria were grown. Yields of 50-93% chlorophyll-a were achieved from the pigment extracts of Synechococcus elongatus, a unicellular cyanobacteria. This material was then digested using concentrated nitric acid to extract magnesium. Separation was accomplished using columns of cation-exchange resin, which achieved a 103 ± 10% yield of magnesium from chlorophyll-a. This procedure ensured accurate measurement of the magnesium-isotopic ratios without isobaric interferences using a multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We find a slight depletion in the heavier isotopes of magnesium in chlorophyll-a relative to culture medium, early growth phase: Δ26Mg = −0.71(±0.35)‰ and Δ25Mg = −0.37(±0.18)‰; late growth phase: Δ26Mg = −0.53(±0.20)‰ and Δ25Mg = −0.26(±0.11)‰, due to an apparent mass-dependent fractionation. We suggest that the small fractionation results from chelation during intracellular processes. A likely candidate for this chelation step involves the magnesium-chelatase enzyme, which mediates the insertion of magnesium to the tetrapyrrole ring during chlorophyll-a biosynthesis. Proof of this hypothesis can be tested with biological controls whereby steps in the enzymatic pathways of chlorophyll synthesis are selectively suppressed.  相似文献   

17.
The sequestration of silicon in soil clay-sized iron oxides may affect the terrestrial cycle of Si. Iron oxides indeed specifically adsorb aqueous monosilicic acid (H4SiO40), thereby influencing Si concentration in soil solution. Here we study the impact of H4SiO40 adsorption on the fractionation of Si isotopes in basaltic ash soils differing in weathering degree (from two weathering sequences, Cameroon), hence in clay and Fe-oxide contents, and evaluate the potential isotopic impact on dissolved Si in surrounding Cameroon rivers. Adsorption was measured in batch experiment series designed as function of time (0-72 h) and initial concentration (ic) of Si in solution (0.61-1.18 mM) at 20 °C, constant pH (5.5) and ionic strength (1 mM). After various soil-solution contact times, the δ30Si vs. NBS28 compositions were determined in selected solutions by MC-ICP-MS (Nu Plasma) in medium resolution, operating in dry plasma with Mg doping with an average precision of ±0.15‰ (±2σSEM). The quantitative adsorption of H4SiO40 by soil Fe-oxides left a solution depleted in light Si isotopes, which confirms previous study on synthetic Fe-oxides. Measured against its initial composition (δ30Si = +0.02 ± 0.07‰ (±2σSD)), the solutions were systematically enriched in 30Si reaching maximum δ30Si values ranging between +0.16‰ and +0.95‰ after 72 h contact time. The enrichment of the solution in heavy isotopes increased with increasing values of three parameters: soil weathering degree, iron oxide content, and proportion of short-range ordered Fe-oxide. The Si-isotopic signature of the solution was partly influenced by Si release, possibly through mineral dissolution and Si desorption from oxide surfaces, depending on soil type, highlighting the complex pattern of natural soils. Surrounding Cameroon rivers displayed a mean Si-isotopic signature of +1.19‰. Our data imply that in natural environments, H4SiO40 adsorption by soil clay-sized Fe-oxides at least partly impacts the Si-isotopic signature of the soil solution exported to water streams.  相似文献   

18.
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   

19.
Boron isotope compositions (δ11B) and B concentrations of rains and snows were studied in order to characterize the sources and fractionation processes during the boron atmospheric cycle. The 11B/10B ratios of instantaneous and cumulative rains and snows from coastal and continental sites show a large range of variations, from −1.5 ± 0.4 to +26.0 ± 0.5‰ and from −10.2 ± 0.5 to +34.4 ± 0.2‰, respectively. Boron concentrations in rains and snows vary between 0.1 and 3.0 ppb. All these precipitation samples are enriched in 10B compared to the ocean value (δ11B = +39.5‰). An empirical rain-vapour isotopic fractionation of +31‰ is estimated from three largely independent methods. The deduced seawater-vapour fractionation is +25.5‰, with the difference between the rain and seawater fractionations principally reflecting changes in the speciation of boron in the liquid with ∼100% B(OH)3 present in precipitations. A boron meteoric water line, δD = 2.6δ11B − 133, is proposed which describes the relationship between δD and δ11B in many, but not all, precipitations. Boron isotopic compositions of precipitations can be related to that of the seawater reservoir by the seawater-vapour fractionation and one or more of (1) the rain-vapour isotopic fractionation, (2) evolution of the δ11B value of the atmospheric vapour reservoir via condensation-precipitation processes (Rayleigh distillation process), (3) any contribution of vapour from the evaporation of seawater aerosols, and (4) any contribution from particulate matter, principally sea salt, continental dust and, perhaps more regionally, anthropogenic sources (burning of biomass and fossil fuels). From the δ11B values of continental precipitations, a sea salt contribution cannot be more than a percent or so of the total B in precipitation over these areas.  相似文献   

20.
We examined oxygen three-isotope ratios of 48 extraterrestrial chromite (EC) grains extracted from mid-Ordovician sediments from two different locations in Sweden, and one location in south-central China. The ages of the sediments (∼470 Ma) coincide with the breakup event of the L chondrite parent asteroid. Elemental compositions of the chromite grains are generally consistent with their origin from L or LL chondrite parent bodies. The average Δ17O (‰-deviation from the terrestrial mass-fractionation line, measured in situ from 15 μm spots by secondary ion mass spectrometry; SIMS) of EC grains extracted from fossil meteorites from Thorsberg and Brunflo are 1.17 ± 0.09‰ (2σ) and 1.25 ± 0.16‰, respectively, and those of fossil micrometeorites from Thorsberg and Puxi River are 1.10 ± 0.09‰, and 1.11 ± 0.12‰, respectively. Within uncertainty these values are all the same and consistent with the L chondrite group average Δ17O = 1.07 ± 0.18‰, but also with the LL chondrite group average Δ17O = 1.26 ± 0.24‰ (Clayton et al., 1991). We conclude that the studied EC grains from correlated sediments from Sweden and China are related, and most likely originated in the same event, the L chondrite parent body breakup. We also analyzed chromites of modern H, L and LL chondrites and show that their Δ17O values coincide with averages of Δ17O of bulk analyses of H, L and LL chondrites. This study demonstrates that in situ oxygen isotope data measured by SIMS are accurate and precise if carefully standardized, and can be used to classify individual extraterrestrial chromite grains found in sediments.  相似文献   

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