Isotopic fractionation of Cu in tektites

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 (δ^66/64Zn 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.     

末元古系-寒武系底Sr、C同位素对比

测定了云南永善肖滩前寒武系-寒武系界限Sr同位素组成及湖北省三峡 剖面震旦系碳酸盐岩Sr、C同位素组成,并与蒙古、 加拿大、西伯利亚和纳米 比亚的末元古系Sr和C同位素数据进行了比较,得出末元古纪海水87Sr/86Sr和 δ13C值的演变图。通过该演变图,可以对全球末元古系地层进行对比。     

Calculation of sulfur isotope fractionation in sulfides

The increment method has been successfully applied to calculate thermodynamic isotope fractionation factors of oxygen in silicates, oxides, carbonates, and sulfates. In this paper, we modified the increment method to calculate thermodynamic isotope fractionation factors of sulfur in sulfides, based on chemical features of sulfur-metal bonds and crystal features of sulfide minerals. To approximate the bond strength of sulfides, a new constant, known as the Madelung constant, was introduced. The increment method was then extended to calculate the reduced partition function ratios of sphalerite, chalcopyrite, galena, pyrrhotite, greenockite, bornite, cubanite, sulvanite, and violarite, as well as the isotope fractionation factors between them over the temperature range from 0 to 1000 °C. The order of ³⁴S enrichment in these nine minerals is pyrrhotite > greenockite > sphalerite > chalcopyrite > cubanite > sulvanite > bornite > violarite > galena. Our improved method constitutes another model for calculating the thermodynamic isotope fractionation factors of sulfur in sulfides of geochemical interest.     

Isotopic composition of sulfur in modern metalliferous hydrotherms in Cheleken

Iron and zinc sulfides, deposited by petroleum brines, are believed to have been derived from terrigenic sedimentary rocks, judging by the isotopic composition of their sulfur, and not from any deposits of these metals in the depths. This view is supported by isotopic analysis of sulfur in brines inside and outside the oil field and in waters of mud volcanoes. Isotopic composition of native (and apparently young) lead, deposited in two of the wells, may likewise represent an epigenetic concentration of the originally dispersed metals in the brines.     

硫化物中硫同位素分馏理论计算研究进展

硫化物是重要的矿物类,通常是一个或多个金属元素与硫结合而形成硫化物.硫化物作为大多数金属的主要来源具有重大的经济利用价值,硫化物中硫同位素分馏的研究一直是同位素地球化学研究的热点.研究不同金属硫化物之间的硫同位素分馏效应,对于利用硫同位素对成矿作用过程和成矿物质来源开展地球化学示踪,具有非常重要的意义.本文结合笔者近期的工作概述了硫化物中硫同位素分馏的理论计算研究,认为虽然半经验半理论的增量方法在同位素分馏计算中存在一定的局限性,但在没有其他实用的理论计算方法时,改进的增量方法可以作为硫化物中硫同位素分馏计算的一种理论估算方法.     

赣东北元古代蛇绿岩Sm—Nd同位素年龄及地质意义

江南古陆东南缘赣东北弋阳—德兴—婺源一线有一条蛇绿岩带,普遍认为它是二个一级大地构造单元的分界线,形成于元古代。推断蛇绿混杂岩是元古代古洋壳俯冲时被挤上来的碎片;也有人认为它是中生代二大古陆之间的缝合线。Sm-Nd矿物等时线给出1034±16Ma(MSWD=1.0)的同位素年龄,它符合元古代缝合带的观点,而不利于中生代缝合带。     

Isotopic composition of pyritic sulfur from the mud volcanic ejecta in Azerbaijan

Geochemical studies of pyrite crystals from the mud volcanic ejecta in Azerbaijan were studied. It is shown that all of them have cubic shape. Determination of the sulfur isotope composition revealed a wide variation range of δ³⁴S values from–27.0 to +26.4‰. Signs of spatial zonation were recorded in the distribution of δ³⁴S values—lower values are confined to the present-day coastline of the Caspian Sea. Appearance of pyrite with a high share of ³⁴S is attributed to sulfate reduction that takes place in an environment with excess organic matter. It is supposed that the isotopically heavy sulfides represent the “neck” facies that are formed at the periphery of mud volcanic conduits at the contact of the hydrocarbon-rich mud volcanic fluids with stratal waters of host sediments.     

A possible boundary condition in bacterial sulfur isotope fractionation

The sulfur isotopic effect (δ³⁴S) shown by batch cultures of six species of sulfate-reducing bacteria was ?14.6%. (S.D.4.1).Fractionation appeared to be independent of electron donor, temperature (between 35 and 55°) and the extent of sulfate reduction.     

Isotopic fractionation during ion filtration: I. Theory

Fractionation of the isotopes of H, O, and Cl during flow of aqueous solutions through semipermeable clay discs has been observed in the laboratory. The observed isotopic abundance trends of these elements in deep sedimentary basins have been attributed to similar phenomena. However, the mechanism responsible for such isotopic fractionation has not been identified. We propose that the fractionation of O and H isotopes in the water molecule results from increased activity of the heavy isotopic species in the membrane solution because high cation concentrations in the membrane pore fluid increase hydrationsphere fractionation effects. The heavy isotopic species thus diffuse away from the membrane and therefore are concentrated behind it. Predictions based on this theory satisfactorily model both laboratory and field observations.We propose that the fractionation of chlorine isotopes is a result of differences in the ionic mobility of ³⁵Cl⁻ and ³⁷Cl⁻. Negative charges on the membrane repel the isotopic species at slightly different velocities against the uniform advective motion of the bulk water and thus the more mobile ³⁵Cl⁻ is enriched behind the membrane. Predictions calculated from this theory compare well with laboratory and field data.     

Isotopic fractionation between coexisting organic carbon—carbonate pairs in Precambrian sediments

δ¹³C_org and δ¹³C_carb values of 58 coexisting organic carbon-carbonate pairs covering the whole Precambrian have yielded means of ?24.7 ± 6.0%. [PDB] and +0.9 ± 2.7%. [PDB], respectively. Accordingly, isotopic fractionation between inorganic and organic carbon in Precambrian sediments is about the same as in geologically younger rocks (Δδ ? 25%.), a slight increase displayed by the Early Precambrian pairs (Δδ ? 28%.) being probably biassed by an over-representation in this age group of samples from one single locality (nevertheless, this value still lies within the range permitted for a possible deviation). It is reasonable to assume, therefore, that the overall isotope fractionation factor governing biological fixation of inorganic carbon has been virtually constant since some 3.3 × 10⁹ yr ago.     

Isotopic fractionation of Kr and Xe implanted in solids at very low energies

We report results on the implantation of Kr and Xe in W under closed system conditions at very low energies (50–500 eV). Investigation of the fraction of gas trapped as a function of time reveals the existence of competing trapping and release mechanisms and analysis of recovered trapped gas and residual gas phases shows that both elemental and isotopic fractionation result from these mechanisms. We determined the mass dependence for the overall implantation process to be at or near m¹, with heavier isotopes enriched in the implanted gas. This mass dependence is inferred to result from implantation and a combination of diffusive and gas sputtering release mechanisms. Our results reaffirm the conclusion of Bernatowicz and Fahey (1986) that previously observed isotopic fractionation of Kr and Xe in carbonaceous material synthesized in electrical discharges owes its origin to low energy ion implantation and also suggest that this process may be relevant to incorporation of noble gases in early solar system materials. We also discuss the implication of our results for noble gas mass spectrometry.     

用改进的增量方法计算硫化物中硫的同位素分馏系数

增量方法已成功地应用到硅酸盐矿物、金属氧化物、碳酸盐矿物和硫酸盐矿物氧同位素分馏系数的计算中。本文在对硫化物晶体结构与矿物学特点分析的基础上,通过详细分析前人对硅酸盐矿物和金属氧化物中氧同位素分馏的增量计算方法,将氧化物和硫化物的晶体特征加以对比,提出了计算硫化物中硫同位素分馏的增量计算方法。修正的增量方法根据硫化物的晶体化学结构特征,引入了一个重要的参数,即Madelung常数,用于指示不同结构的硫化物对~(34)S的富集能力。本文利用这一修正的增量方法计算出了0℃到1000℃温度范围内,磁黄铁矿、方铅矿、闪锌矿、黄铜矿、硫镉矿的10~3Inβ和它们之间的分馏系数10~3Inα。并给出这五种矿物间的~(34)S富集顺序：磁黄铁矿＞硫镉矿＞闪锌矿＞黄铜矿＞方铅矿。与前人的实验结果对比表明,本次计算结果与实验结果基本吻合。同时,增量计算方法成功地再现了任意硫化物中~(32)S、~(33)S、~(34)S和~(36)S这四种同位素之间确实存在一定的分馏比例关系。这说明尽管增量方法存在一定的局限性,但将其扩展到硫化物间硫同位素分馏的理论计算是可行的。     

Isotopic fractionation of the major elements of molten basalt by chemical and thermal diffusion

Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter Ω_i defined as the fractionation in per mil per 100 °C per atomic mass units difference between the isotopes. For molten basalt we report Ω_Ca = 1.6, Ω_Fe = 1.1, Ω_Si = 0.6, Ω_O = 1.5. In an earlier paper we reported Ω_Mg = 3.6. These fractionations represent a steady state balance between thermal diffusion and chemical diffusion with the mass dependence of the thermal diffusion coefficient being significantly larger than the mass dependence of the chemical diffusion coefficients for isotopes of the same element. The iron isotopic measurements of the basalt-rhyolite diffusion couple showed significant fractionation that are parameterized in terms of a parameter β_Fe = 0.03 when the ratio of the diffusion coefficients D₅₄ and D₅₆ of ⁵⁴Fe and ⁵⁶Fe is expressed in terms of the atomic mass as D₅₄/D₅₆ = (56/54)^β_Fe. This value of β_Fe is smaller than what we had measured earlier for lithium, magnesium and calcium (i.e., β_Li = 0.215, β_Ca = 0.05, β_Mg = 0.05) but still significant when one takes into account the high precision with which iron isotopic compositions can be measured (i.e., ±0.03‰) and that iron isotope fractionations at magmatic temperatures from other causes are extremely small. In a closing section we discuss technological and geological applications of isotopic fractionations driven by either or both chemical and thermal gradients.     

Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles

Sulfur isotope studies of post-Archean terrestrial materials have focused on the ratio ³⁴S/³²S because additional isotopes, ³³S and ³⁶S, were thought to carry little information beyond the well-known mass-dependent relationship among multiple-isotope ratios. We report high-precision analyses of Δ³³S and Δ³⁶S values, defined as deviations of ³³S and ³⁶S from ideal mass-dependent relationships, for international reference materials and sedimentary sulfides of Phanerozoic age by using a fluorination technique with a dual-inlet isotope ratio mass spectrometer. Measured variations in Δ³³S and Δ³⁶S are explained as resulting from processes involve branching reactions (two or more reservoirs formed) or mixing. Irreversible processes in closed systems (Rayleigh distillation) amplify the isotope effect. We outline how this new isotope proxy can be used to gain new insights into fundamental aspects of the sulfur biogeochemical cycle, including additional constraints on seawater sulfate budget and processes in sedimentary sulfide formation. The isotope systematics discussed here cannot explain the much larger variation of Δ³³S and Δ³⁶S observed in Archean rock records. Furthermore, Phanerozoic samples we have studied show a characteristic Δ³³S and Δ³⁶S relationship that differs from those measured in Archean rocks and laboratory photolysis experiments. Thus, high precision analysis of Δ³³S and Δ³⁶S can be used to distinguish small non-zero Δ³³S and Δ³⁶S produced by mass-dependent processes from those produced by mass-independent processes in Archean rocks and extraterrestrial materials.     

Isotopic composition of sulfur in stratified deposits of copper ores in Olekma-Vitim montane area

Striking preponderance of the light isotopes and a very wide range of variation (δS³⁴ from +13.5 to -21.8) are typical of the isotopic composition of sulfidic sulfur in copper ore deposits of the area, even as they are in the case of analogous ore deposits elsewhere. Fluctuations in the isotopic composition of sulfur in profiles of cupriferous rocks and parts thereof are explainable by specificities in physicochemical environments of the sediment-water-organic substance system. -- Authors.     

Isotopic fractionation: A kinetic model for crystals growing from magmatic melts

Recent experiments in the fields of crystal growth, crystal-melt element partitioning, and diffusion in magmatic melts make it possible to estimate disequilibrium partitioning for many species between liquid and crystals and to compute quantitative models which take into account partition coefficients, diffusivities and rates of crystal growth. A slight difference in the diffusivities of two isotopes should lead to selective depletion (or enrichment) in the crystals as they grow, resulting in varying isotopic ratios as crystallization proceeds. Reasonable hypotheses permit under general kinetic conditions an estimation of magnitude of possible effects. The resulting isotopic fractionation for major elements (like oxygen) may exceed the per ml level; for trace elements the effects may be more significant (5–10 per ml), especially in the case of low partition coefficients, but analytical difficulties are formidable at present.     

Geological and Isotopic Constraints on the Metallogenic Evolution of the Proterozoic Sediment-Hosted Pb-Zn (Ag) Deposits of Brazil

Integrated studies of seven Proterozoic sediment-hosted, Pb-Zn-Ag sulfide deposits of Brazil, permit the estimation of the age of the hosting sequence and the mineralization, the nature of the sulfur and metal sources, the temperature range of sulfide formation and the environment of deposition. These deposits can be classified into three groups, according to their ages. (a) Archean to Paleoproterozoic: the Boquira deposit, in Bahia state, consists of stratiform massive and disseminated sulfides hosted by parametamorphic sequences of grunnerite-cummingtonite+magnetite that represent a silicate facies of the Boquira Formation (BF). Lead isotope data of galena samples indicate a time span between 2.7 and 2.5 Ga for ore formation, in agreement with the stratigraphic position of the BF. The relatively heavy sulfur isotope compositions for the disseminated and stratiform sulfides (+8.3 to +12.8 ‰ CDT)suggest a sedimentary source for the sulfur. (b) Paleo to Mesoproterozoic: stratiform and stratabound sulfides in association with growth faults are present in the Canoas mine (Ribeira, in Paraná state) and in the Caboclo mineralization (Bahia state). They are hosted by calcsilicates and amphibolites in the Canoas deposit, whereas in the Caboclo area the mineralization is associated with hydrothermally altered dolarenites at the base of the 1.2 Ga Caboclo Formation. The interpreted Pb-Pb age of the Canoas mineralization is coeval with the 1.7 Ga host rocks. Sulfur isotopic data for Canoas sulfides (+1.2 to +16 ‰ CDT) suggest a sea water source for the sulfur. The range between −21.1 and +8.8 ‰ CDT for the Caboclo sulfides could suggest the action of bacterial reduction of seawater sulfates, but this interpretation is not conclusive. (c) Neoproterozoic: stratiform and stratabound sulfide deposits formed during the complex diagenetic history of the host carbonate rocks from the Morro Agudo (Bambui Group), Irecê and Nova Redenção (Una Group), yield heavy sulfur isotope values (+18.9 to +39.4 ‰ CDT). The uniform heavy isotope composition of the barites from these deposits (+25.1 to +40.9 ‰) reflect their origin from Neoproterozoic seawater sulfates. The late-stage, and most important, metallic concentrations represent sulfur scavenged from pre-existing sulfides or from direct reduction of evaporitic sulfate minerals. Lead isotope data from the Bambui Group suggest focused fluid circulation from diverse Proterozoic sediment sources, that probably was responsible for metal transport to the site of sulfide precipitation. (d) Late Proterozoic to Early Paleozoic: lead-zinc sulfides (+pyrite and chalcopyrite) of Santa Maria deposits, in Rio Grande do Sul, form the matrix of arkosic sandstones and conglomerates, and are closely associated with regional faults forming graben structures. Intermediate volcanic rocks are intercalated with the basal siliciclastic members. Lead isotope age of the mineralization (0.59 Ga) is coeval with the host rocks. Sulfur isotopic values between −3.6 and +4.1 are compatible with a deep source for the sulfur.Geological, petrographic and isotopic data of the deposits studied suggest that they were formed during periods of extensional tectonics. Growth faults or reactivated basement structures probably were responsible for localized circulation of metal-bearing fluids within the sedimentary sequences. Sulfides were formed by the reduction of sedimentary sulfates in most cases. Linear structures are important controls for sulfide concentration in these Proterozoic basins.     

Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin

Sulfur isotope composition (δ³⁴S) profiles in sediment pore waters often show an offset between sulfate and sulfide much greater in magnitude than S isotope fractionations observed in pure cultures. A number of workers have invoked an additional reaction, microbial disproportionation of sulfur intermediates, to explain the offset between experimental and natural systems. Here, we present an alternative explanation based on modeling of pore water sulfate and sulfide concentrations and stable isotope data from the Cariaco Basin (ODP Leg 165, Site 1002B). The use of unique diffusion coefficients for and , based on their unequal molecular masses, resulted in an increase in the computed fractionation by almost 10‰, when compared to the common assumption of equal diffusion coefficients for the two species. These small differences in diffusion coefficients yield calculated isotopic offsets between coeval sediment pore water sulfate and sulfide without disproportionation (up to 53.4‰) that exceed the largest fractionations observed in experimental cultures. Furthermore, the diffusion of sulfide within sediment pore waters leads to values that are even greater than those predicted by our model for sulfate reduction with unique diffusion coefficients. These diffusive effects on the sulfur isotope composition of pore water sulfate and sulfide can impact our interpretations of geologic records of sulfate and sulfide minerals, and should be considered in future studies.     

Isotopic composition of sulfur and genesis of copper ores of Zdhezkazgan and Udokan

Enrichment of S³² in sulfidic sulfur and large variations in δS³⁴ content of certain minerals are characteristic of the ores. It is possible therefore that their sulfur was derived from sedimentary rocks and that bacterial reduction of sedimentary sulfates had a part in the process. The isotopic composition of sulfidic sulfur in cupriferous sandstones and in the veinlets therein is about the same. Consequently, a borrowing a sulfur by the veinlets from the sandstones appears to be a reasonable assumption. A biogenic-sedimentary origin of the sulfides does not preclude accessions of copper and other metals from the magma. -- Author.