Isotopic composition of zinc, copper, and iron in lunar samples

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ⁶⁶Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ⁶⁵Cu  +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ⁵⁶Fe = −0.24‰, δ⁶⁵Cu = −0.42‰, and δ⁶⁶Zn  −3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰  δ⁵⁶Fe  0.51‰, 2.6‰  δ⁶⁵Cu  4.5‰, and 2.2‰  δ⁶⁶Zn  6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.     

Determination of mass-dependent molybdenum isotopic variations by MC-ICP-MS: An evaluation of matrix effects

Several analytical techniques are currently used to determine mass-dependent molybdenum isotopic variations in natural materials using multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), including different methods for the separation of Mo from the sample and the correction for instrumental mass-dependent isotopic fractionation (instrumental mass bias). Both internal (“double-spiking” using two enriched Mo isotopes) and external (“zirconium doping” with standard-sample bracketing) techniques have been used in previous studies to deal with the effects of instrumental mass bias. The results of these studies have indicated that the precision for Mo isotopic analyses of natural (matrix-bearing) samples is a factor of ∼4–7× better using a double spike. Here we present a detailed study of the ability of MC-ICP-MS to determine, both precisely and accurately, the isotopic composition of Mo extracted from molybdenite using a low blank, high yield two-column procedure for Mo separation and a simple standard-sample bracketing approach to correct for instrumental mass bias. Based on analyses of molybdenites, the precision of this technique is shown to be similar to published double-spike data (within a factor of ∼2). All three of the known types of potential matrix effects in the MC-ICP-MS are also evaluated: automatrix effects, matrix effects due to Zr doping and matrix effects due to elements in the sample other than Mo and Zr. Each of these matrix effects is found to be either insignificant or controllable. Analyses of five molybdenites of hydrothermal origin reveal a range in their Mo isotopic composition that is a factor of ∼4 greater than the previous range reported for such samples. More detailed work is required to elucidate the origin of these mass-dependent Mo isotopic variations in molybdenites.     

MC-ICP-MS测定积累植物中Cu、Zn同位素的化学分离方法研究

多接收器等离子体质谱仪(MC-ICP-MS)高精度同位素组成的准确测定,依赖于对样品中待测元素的分离纯化.本研究比较了两种溶样方法对有机样品积累植物海州香薷的消解效果,检测了AG MP-1阴离子交换树脂对样品中Cu、Zn的分离效果,并测定了样品中的Cu、Zn同位素组成.结果表明:①两种不同溶样方法均能有效地破坏累植物海州香薷样品中的有机质;②AG MP-1树脂能有效分离纯化植物中的Cu、Zn,经过AG MP-1树脂一次交换分离和二次交换分离的植物根样品的Cu接收液基体元素的去除基本没有差别,经过一次交换分离的Zn溶液,基体元素也基本除去,可以用于MC-ICP-MS对Cu、Zn同位素组成高精度的测定;③Cu、Zn同位素组成测定误差不大于仪器的长期重现性,表明样品的化学处理过程、各离子交换树脂柱分离交换过程和仪器测试过程均有很好的重现性,符合样品测定的要求.     

多接收电感耦合等离子体质谱(MC-ICPMS)测量铜、锌、铁的同位素组成及其地质意义

Cu、Zn、Fe同位素示踪是近年来发展起来的一项新兴的同位素地球化学方法。本文介绍了用多接收电感耦合等离子体质谱 (MC ICPMS)精确测量铜、锌、铁同位素比值的方法 ,发现这些元素的同位素组成在不同地质与成矿环境中有明显变异 ,因而它们在矿床学、古海洋学和生物学等诸多领域具有广泛的应用前景。     

Isotopic and geochemical studies on crustal effects in the genesis of the woodlawn Pb-Zn-Cu deposit

Lead (and U-Pb) isotope data for sulphides and whole rocks, U-3Pb data for zircons, and Rb-Sr data for whole rocks have been determined in an attempt to elucidate the processes by which the volcanic Pb-Zn-Cu deposit at Woodlawn, southeastern N.S.W., was formed, and to relate this information to current theories of crustal effects in the genesis of volcanic Pb-Zn deposits.The lead isotope compositions of pyrite, galena, sphalerite, and chalcopyrite from the ore horizon are the same, and identical to the initial lead isotope compositions of pyrite in the host volcanics.Linear relations are obtained for plots of ²⁰⁷Pb/ ²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb vs ²⁰⁴Pb/²⁰⁴Pb, and ²³⁸U/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb for least altered whole rock volcanics, indicating no loss or gain of U to these rocks since their formation. The similar initial ²⁰⁶Pb/²⁰⁴Pb ratios in the sulphides and host volcanics suggest a common source for the lead. However, acid leach experiments, carried out to remove the ore lead influence, suggest the lead to be a complex mixture of ore and rock lead. The differences observed for high and low lead samples in the acid leaching experiments suggest that these tests may provide an additional tool in prospecting for base-metal sulphides of this type.U-Pb data for zircons from the whole rocks give a spectrum of apparent ages ranging from 428 to 477 m.y. reflecting varying amounts of older zircons or resetting of the U-Pb systems in the volcanics. The older zircons are present either as discrete rounded crystals or cores surrounded by new euhedral growth. The populations and U-Pb data suggest the rocks were pre-existing volcanics with a possible detrital component, whose ages have not been fully reset during remelting.In contrast to the zircon data, U-Pb and Rb-Sr whole rock data define lines proportional to ages of 413±6 m.y. and 409±4 m.y. (1.39×10^–11/yr) respectively and the strontium has a relatively high initial ratio of 0.710.The complex zircon population, high initial Sr ratio, Th/U ratios and rare earth data suggest the Woodlawn volcanics were formed by multistage remelting of material of similar chemical composition. Consequently, conformable deposits of this type should not be discussed in terms of the Growth Curve and single stage models of lead development.Mineralization is thought to have occurred at 420 m.y., either from solutions associated with the volcanism and/or concentrated from the volcanics and sediments by circulating sea water, in a shallow convective cell and soon after, or during, the formation of the pile. Alternatively, the multistage processes operating during formation of the Woodlawn volcanics acted as an effective homogeniser of lead isotopes.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

The effects of temperature,pressure, and oxygen on copper and iron sulphides synthesised in aqueous solution

Experiments with both iron sulphide and copper sulphide precipitates in aqueous solution show that oxygen is significant in determining the mineral phases resulting after heating up to 180 °C. Tetragonal FeS converts to FeS₂ and Fe₃O₄ in the presence of oxygen, while in the absence of oxygen under the same conditions it converts to hexagonal FeS. Suspensions of covellite and of chalcocite under the same conditions convert to digenite in the presence of oxygen, but remain unchanged when oxygen is absent. Experimental evidence is advanced to support structure determinations that CuS contains disulphide ions.

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Zusammenfassung Experimente mit in wässrigen Lösungen ausgefällten Eisen- und Kupfersulfiden dokumentieren die außerordentliche Bedeutung des Sauerstoffes auf die Bildungs- und Verhaltensweise von Mineralphasen, beobachtet nach dem Aufheizen auf 180 °C. So bildet sich aus ursprünglich tetragonalem FeS letzten Endes Pyrit und Magnetit, wenn Sauerstoff zugegen war, während bei dessen Abwesenheit, aber sonst gleichen Versuchsbedingungen, die Umwandlung in hexagonales FeS erfolgte. Suspensionen von Covellin und Chalkosin wurden, unter analogen Versuchsbedingungen und in Gegenwart von Sauerstoff, in Digenit überführt, während sonst, wenn keine Sauerstoffeinwirkung stattfand, die Mineralphasen keinerlei Veränderungen erkennen ließen. Mittels solcher experimenteller Methoden lassen sich bei der Strukturbestimmung des CuS offenbar Merkmale des Vorhandenseins von Disulfidionen erkennen.

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Published by permission of the Director, Bureau of Mineral Resources, Canberra A. C. T., Australia.

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Temporary Address: Mineralog.-Petrograph. Inst. Univ. Heidelberg, Berliner Str. 19, 69 Heidelberg, Germany     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Investigation of copper minerals by NQR: Crystallochemistry,electronic structure,lattice dynamics

A series of copper minerals has been investigated by NQR (Nuclear Quadrupole Resonance), the most typical cases of Cu(I) environment in oxides, sulphides and sulphosalts being taken into account. The linear complexes CuX ₂ have the greatest quadrupole splitting. Minimal quadrupole splitting is observed in tetrahedral complexes. Spin-lattice relaxation measurements indicate that the quadrupole relaxation mechanism due to the Raman process predominates.     

Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary

The present study evaluates several critical issues related to precision and accuracy of Cu and Zn isotopic measurements with application to estuarine particulate materials. Calibration of reference materials (such as the IRMM 3702 Zn) against the JMC Zn and NIST Cu reference materials were performed in wet and/or dry plasma modes (Aridus I and DSN‐100) on a Nu Plasma MC‐ICP‐MS. Different mass bias correction methods were compared. More than 100 analyses of certified reference materials suggested that the sample‐calibrator bracketing correction and the empirical external normalisation methods provide the most reliable corrections, with long term external precisions of 0.06 and 0.07‰ (2SD), respectively. Investigation of the effect of variable analyte to spike concentration ratios on Zn and Cu isotopic determinations indicated that the accuracy of Cu measurements in dry plasma is very sensitive to the relative Cu and Zn concentrations, with deviations of δ⁶⁵Cu from ?0.4‰ (Cu/Zn = 4) to +0.4‰ (Cu/Zn = 0.2). A quantitative assessment (with instrumental mass bias corrections) of spectral and non‐spectral interferences (Ti, Cr, Co, Fe, Ca, Mg, Na) was performed. Titanium and Cr were the most severe interfering constituents, contributing to inaccuracies of ?5.1‰ and +0.60‰ on δ^68/64Zn, respectively (for 500 μg l^?1 Cu and Zn standard solutions spiked with 1000 μg l^?1 of Ti or Cr). Preliminary isotopic results were obtained on contrasting sediment matrices from the Scheldt estuary. Significant isotopic fractionation of zinc (from 0.21‰ to 1.13‰ for δ⁶⁶Zn) and copper (from ?0.38‰ to 0.23‰ for δ⁶⁵Cu), suggest a control by physical mixing of continental and marine water masses, characterized by distinct Cu and Zn isotopic signatures. These results provide a stepping‐stone to further evaluate the use of Cu and Zn isotopes as biogeochemical tracers in estuarine environments.     

四川省拉拉铜矿床同位素地球化学特征及成矿意义

拉拉铜矿床位于康滇地轴西南缘,赋矿围岩是古元古界变质火山岩。通过矿床硫同位素、氢氧同位素、K-Ar同位素、铅同位素、Rb-Sr同位素及辉钼矿中Re-Os同位素的组成特点讨论了成矿时代、物质来源、成矿介质性质及矿床成因等问题。新元古代晋宁期发生的区域变质作用是促使矿床形成的主要成矿作用,古元古代形成的火山岩提供了大部分的成矿物质来源,成矿介质以变质水为主后期有大量地下水的加入。矿床为火山沉积-变质成因的层控型铜矿床。     

云南格咱岛弧带休瓦促Mo W Cu矿床两期岩浆作用的锆石U Pb年龄、Hf同位素组成及构造意义

锆石LA-ICP-MS U-Pb定年结果显示,休瓦促Mo-W-Cu矿床含矿花岗闪长岩的形成年龄为202±3.5Ma,形成于甘孜-理塘洋壳向西俯冲时期;含矿二长花岗岩的形成年龄为83.3±1.7Ma,形成于燕山晚期造山后伸展环境。Hf同位素原位分析结果显示,花岗闪长岩中锆石的ε_(Hf)(t)值为-2.87~4.12(平均为0.09),T_(MD1)年龄541~828Ma,T_(DM2)年龄为719~1109Ma,表明岩体形成的物质来源除壳源物质之外,也有幔源物质的混入;二长花岗岩中锆石的ε_(Hf)(t)值为-7.96~-2.75(平均为-5.54),T_(MD1)年龄为820~1019Ma,T_(DM2)年龄为1102~1391Ma,ε_(Hf)(t)0,表明岩石是由古老地壳物质的部分熔融形成的产物。休瓦促两期含矿岩体的锆石U-Pb定年与Hf同位素原位分析显示,区内存在晚三叠世和晚白垩世两期构造-岩浆-成矿作用。晚三叠世花岗闪长岩岩浆侵入及Cu多金属成矿作用与洋壳俯冲造山有关;而晚白垩世二长花岗岩岩浆侵入及Mo多金属成矿作用主要形成于陆-陆碰撞造山的构造背景。研究表明,从晚三叠世洋壳俯冲造山至晚白垩世造山后伸展作用过程中都存在构造-岩浆-成矿作用的发生,且在晚三叠世构造-岩浆活动的基础上叠加了晚白垩世的成岩成矿作用,这为区内复合叠加成矿作用的研究提供了例证。     

苯、甲苯对粒状铁去除四氯乙烯影响的柱实验研究

挥发性氯代烃和石油烃类污染是地下水中最常见的混合污染类型,而且这两类污染物毒性极强,对人类危害非常严重。文中选取具有代表性的四氯乙烯、苯和甲苯为研究对象,采用柱实验的方法研究苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除四氯乙烯的机理及反应动力学的影响。在实验装置运行的过程中,苯、甲苯和四氯乙烯的浓度始终控制在2mg/L左右的水平。实验结果表明:苯或甲苯的存在对被还原的产物组成没有影响,主要氯代中间产物均为TCE、1,1-DCE、cis-1,2-DCE和VC,但组成比例略有不同。苯和甲苯的存在对去除速率有影响,即苯对四氯乙烯的去除有促进作用,去除速率平均提高13.5%;而甲苯则抑制四氯乙烯的去除,去除速率平均降低13.8%。对比控制柱,苯和甲苯存在时对出水水化学变化的影响没有明显差异。     

Isotopic fractionation of iron, potassium, and oxygen in stony cosmic spherules: Implications for heating histories and sources

Atmospheric heating alters the compositions and textures of micrometeorites. To understand the changes and to test a proposed relationship between a micrometeorite’s petrographic texture and its degree of heating, we made elemental and multiple isotope analyses of stony cosmic spherules (sCS) collected from the South Pole Water well. Specifically, we analyzed the elemental compositions of 94 sCS and the isotopic ratios of Fe, K and O, on 43, 12 and 8 of these sCS, respectively.Our results show that sCS classified as strongly heated generally have lower concentrations of volatile and moderately volatile elements. Of the 43 spherules analyzed for Fe isotopes, only 5 have δ⁵⁷Fe >5‰. In contrast, enrichment of ⁴¹K is pervasive (δ⁴¹K >0 in all 12 spherules analyzed) and large (up to 183‰). The determination of K isotope abundances in sCS may therefore be useful in deciphering thermal histories. Three of the eight sCS analyzed for O isotopes are mass fractionated with δ¹⁸O >30‰. We attribute two of these three δ¹⁸O enrichments to evaporative losses of oxygen in the atmosphere and the third to the presence in the parent material of an exotic phase, perhaps a sulfate or a carbonate. The K isotope and O isotope data are broadly consistent with the proposed textural classification.Because most spherules were not heated enough to fractionate Al, Mg, or Si, we compared the measured Mg/Al and Si/Al ratios directly to those of conventional meteorites and their matrices. ∼30% of the sCS have compositions outside the range defined by the bulk and the matrix compositions of known meteorite groups but consistent with those of pyroxene- and olivine-rich materials and may be samples of chondrules. The other 70% have Mg/Al and Si/Al ratios similar to those of CI, CM, CO, and CV chondrites. Natural variability of the Mg/Al and Si/Al ratios precludes the assignment of an individual sCS to a particular class of C-chondrite.     

兰坪-思茅盆地砂页岩中铜矿床同位素地球化学

兰坪－思茅中新生代盆地中的铜矿床,主要产于同砂岩、粉砂岩和页岩组成的含盐红色碎屑岩建造中。对矿床的同位素组成研究表明：成矿溶液主要来自大气降水,矿蚀变作用是在水／岩比值较低的体系中进行的;铅来自赋矿的沉积与基底岩石的混合;硫、碳和硅则具有多来源的特性。矿床地质特征和同位素组成特点表明,所研究的铜矿床与典型砂页岩型铜矿床存在显著差异,而与一些地热区的矿化作用相似。说明研究区砂页岩中的铜矿床具有特殊的     

新疆巴仑台铁铜矿床地质特征与成矿作用探讨

新疆巴仑台铁铜矿赋存于华力西期中酸性侵入岩与碳酸盐的接触带上,矿体形态以似层状、透镜状为主。围岩蚀变主要有矽卡岩化、绿泥石化、绿帘石化、硅化。矿石矿物以磁铁矿、黄铁矿、黄铜矿为主,脉石矿物中有典型的矽卡岩矿物透辉石、石榴子石。矿床成因类型为矽卡岩型。该矿床的成矿作用主要为热液交代作用,其过程分为矽卡岩期、石英硫化物期和表生期3个成矿时期。     

Pb Isotopic Composition and Metal Sources of Au and Ag Deposits of the South Verkhoyansk Region (Yakutia,Russia) According to High-Precision MC-ICP-MS Data

The paper considers the results of high-precision Pb–Pb isotopic analysis of 120 galena samples from 27 Au and Ag deposits of the South Verkhoyansk Synclinorium (SVS) including large Nezhdaninsky deposit (628.8 t Au). The Pb isotopic composition is analyzed on a MC-ICP-MS NEPTUNE mass-spectrometer from solutions with an error of no more than ±0.02% (2σ). Four types of deposits are studied: (i) stratified vein gold–quartz deposits (type 1) hosted in metamorphosed Upper Carboniferous–Lower Permian terrigenous rocks and formed during accretion of the Okhotsk Block to the North Asian Craton synchronously with dislocation metamorphism and related granitic magmatism; (ii) vein gold–quartz (Nezhdaninsky type) deposits also hosted in Lower Permian metasedimentary rocks; (iii) Au–Bi deposits localized at the contact zones of the Late Cretaceous granitic plutons; and (iv) Sn–Ag polymetallic deposits related to granitic and subvolcanic rocks of the Okhotsk Zone of the SVS. The deposits of types 2, 3, and 4 are postaccretionary. The general range of ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios is 18.1516–18.5903 (2.4%), 15.5175–15.6155 (0.63%), and 38.3010–39.0481 (2.0%), respectively. In ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb–²⁰⁸Pb/²⁰⁴Pb diagrams, the data points of Pb isotopic compositions of all deposits occupy restricted, partly overlapping areas along a general elongated trend. The various SVS Au–Ag deposits can be classified according to the Pb isotopic composition in accordance with all three Pb ratios. Deposits of the same type show distinct Pb isotopic compositions that strongly exceed the scale of analytical error (±0.02%). The differences in Pb isotopic composition within specific deposits are low and subordinate and have little effect on variations in the Pb isotopic composition of the SVS deposits. The μ₂ values (Stacey–Kramers model), which characterize the ²³⁸U/²⁰⁴Pb ratios of ore lead sources of the SVS deposits, widely vary from 9.7 to 9.38. The ω₂ values (²³²Th/²⁰⁴Pb) are 39.82–36.61, whereas the Th/U ratios are 4.04–3.86. The content of all three radiogenic Pb isotopes and μ₂ values of feldspars from SVS intrusive rocks are strongly distinct from those of galena of stratified gold–quartz and vein gold–quartz deposits and are identical to Pb of galena from Au–Bi and Sn–Ag polymetallic deposits, indicating a mostly magmatic origin for the Pb of these deposits. Detailed isotopic study of the Nezhdaninsky deposit shows different Pb isotopic composition of two consecutive mineral assemblages (gold–sulfide and Ag polymetallic): ~0.30, ~0.07, and ~0.22% for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. These differences are interpreted as a result of involvement of at least two metal sources during the evolution of an ore-forming system: (i) host Lower Permian terrigenous rocks and (ii) a magmatic source similar in Pb isotopic composition to that of Sn–Ag polymetallic deposits. The Pb isotopic composition and μ₂ and Th/U values show that lead of stratified gold–quartz deposits combines isotopic tracers of lower and upper crustal sources (Upper Carboniferous–Lower Permian terrigenous rocks), lead of which was mobilized by ore-bearing fluids. The high ²⁰⁸Pb/²⁰⁶Pb ratios and Th/U evolutionary parameter are common to all Pb isotopic composition of all studied Au–Ag deposits and SVS Cretaceous intrusive rocks and indicate that Pb sources were depleted in U relative to Th. Taking into account the structure of the region and conceptions on its evolution, we can suggest that the magma source was related to lower crustal subducted rocks of the Archean (~2.6 Ga) North Asian Craton and the Okhotsk terrane.     

A Strontium and Neodymium Isotopic Investigation of the Fongen--Hyllingen Layered Intrusion, Norway

The Fongen—Hyllingen Intrusion, situated 60 km SE of Trondheim,Norway, is a synorogenic layered mafic intrusion of Caledonianage . The intrusion is divided into four evolutionary stages based on cryptic variations: StageI—a basal reversal; Stage II—unchanged mineral chemistryor slight normal evolution; Stage III—a gradual regression;Stage IV— a strong normal fractionation trend Magma replenishmentdominated during most of the crystallization, i.e. during StagesI, II and III Replenishing magma was more dense than resident,evolved magma, and continuing influx eventually caused a compositionallystratified magma column to form. Cryptic lateral variation isan important feature in the southern part of the complex andformed by in situ crystallization from a stratified magma alongan inclined floor, where modal layering formed parallel to thecrystallization front. Initial Sr- and Nd-isotopic ratios inthe cumulates vary as a result of assimilation of country rockand subsequent mixing between uncontaminated, replenishing magmaand contaminated, resident magma. The parental magma had a moderatelydepleted isotope composition, relative to Bulk Earth, with _Nd=584and Sr_i=070308, whereas the main contaminant was a partialmelt of metapelitic country rock with _Nd=-874 and Sr_i=07195(Sr_i is the initial ⁸⁷Sr/⁸⁶Sr). Sr_i in the analysed cumulatewhole-rock samples ranges from 070308 to 070535 and initial_Nd ranges from. 158 to 584. There is a strong correlationbetween mineralogical composition and isotopic trends in mostof the cumulates: the most primitive samples are the least contaminated,as reflected by relatively high ed and low Sr,, and more evolvedsamples have progressively lower eNi and higher Sry A gradualregression of several hundred metres thickness characterizesStage III; stratigraphically upwards mineral compositions becomemore primitive and isotope compositions more depleted (higher_Nd and lower Sr_i), implying a process of. progressive mixing-inof replenishing, primitive and uncontaminated magma. Magma influxin Stage III took place by fountaining, whereas magma additionwas more tranquil in the earlier stages. The fountaining influxentrained resident, relatively evolved and contaminated magma,resulting in a hybrid magma which ponded at the floor. Duringprolonged magma addition with concomitant crystallization, thelowermost magma layer was replaced by progressively more primitivehybrid magma, creating a gradual regression in the crystallizingcumulate sequence. A detailed two-dimensional study revealslateral variations in mineral compositions both at the baseand top of Stage III, whereas lateral variations in Sr- andNd-isotopic compositions are present at the top, but not atthe base. This implies that the lowest crystallizing part ofthe magma column was essentially isotopically homogeneous, butcompositionally stratified, before influx in Stage III. Isotopicgradients in the magma were strong close to the roof, wheremost of the assimilation occurred, and decreased downwards,merging into isotopically homogeneous magma. This stratifiedsystem was destroyed by turbulent mixing between replenishingand resident magma during fountaining influx in Stage III, anda new stratification was established with both an isotopic anda compositional gradient. After the final influx, crystallizationcontinued in an essentially closed system, in which the remainingmagma column eventually became homogenized, as magma layersmixed when their densities converged owing to release of buoyant,residual liquid during fractional crystallization. Corresponding author