Ban-1 Zircon: A New Natural Zircon Reference Material for LA-MC-ICP-MS Zr and Hf Isotopic Determinations

New zircon reference materials for in situ zircon radiogenic Hf isotope and stable Zr isotopic determinations made by laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) are required due to high data productivity and consequently high reference material consumption rate. This study examines a new natural zircon for Zr isotope ratios by double spike thermal ionisation mass spectrometry (TIMS), and for Hf isotopes by bulk solution nebuliser (SN)-MC-ICP-MS with both Zr and Hf determined by LA-MC-ICP-MS. A total of five zirconium isotope measurements from drilled zircons, determined by TIMS, yield a mean δ^94/90Zr_IPGP-Zr value of -0.09 ± 0.06‰ (2s). Five and eight hafnium isotope measurements for powders from the drilled zircons and Ban-1-4 by SN-MC-ICP-MS, yield mean ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.282985 ± 0.000011 (2s) and 0.282982 ± 0.000007 (2s), respectively. The mean δ^94/90Zr_IPGP-Zr value and ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by LA-MC-ICP-MS analyses are -0.06 ± 0.09‰ (2s, n = 504) and 0.282985 ± 0.000035 (2s, n = 327), respectively. The isotopic homogeneities suggest that the Ban-1 zircon is a suitable reference material for microbeam Zr and Hf isotopic measurements.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

Genesis of the Maoling gold deposit in the Liaodong Peninsula: Constraints from a combined fluid inclusion,C-H-O-S-Pb-He-Ar isotopic and geochronological studies

The large tonnage Maoling gold deposit (25 t @ 3.2 g/t) is located in the southwest Liaodong Peninsula, North China Craton. The deposit is hosted in the Paleoproterozoic metamorphic rocks. Four stages of mineralization were identified in the deposit: (stage I) quartz-arsenopyrite ± pyrite, (stage II) quartz-gold- arsenopyrite-pyrrhotite, (stage III) quartz-gold- polymetallic sulfide, and (stage IV) quartz-calcite-pyrrhotite. In this paper, we present fluid inclusion, C-H-O-S-Pb-He-Ar isotope data, zircon U-Pb, and gold-bearing sulfide (i.e. arsenopyrite and pyrrhotite) Rb-Sr age of the Maoling gold deposit to constrain its genesis and ore-forming mechanism. Three types of fluid inclusions were distinguished in quartz-bearing veins, including liquid-rich two-phase (WL type), gas-rich two-phase (GL type), and daughter mineral-bearing fluid inclusions (S type). Fluid inclusions data show that the homogenization at temperatures 197 to 372 °C for stage I, 126 to 319 °C for stage II, 119 to 189 °C for stage III, and 115 to 183 °C for stage IV, with corresponding salinities of 3.7 to 22.6 wt.%, 4.7 to 23.2 wt.%, 5.3 to 23.2 wt.%, and 1.7 to 14.9 wt.% NaCl equiv., respectively. Fluid boiling was the critical factor controlling the gold and associated sulfide precipitation at Maoling. Hydrogen and oxygen stable isotopic analyses for quartz yielded δ¹⁸O = ?5.0‰ to 9.8‰ and δ D = ?133.5‰ to ?77.0‰. Carbon stable isotopic analyses for calcite and ankerite yielded δ¹³C = ?2.3‰ to ?1.2‰ and O = 7.9‰ to 14.1‰. The C-H-O isotope data show that the ore-forming fluids were originated from magmatic water with meteoric water input during mineralization. Hydrothermal inclusions in arsenopyrite have ³He/⁴He ratios of 0.002 Ra to 0.054 Ra, and ⁴⁰Ar/³⁶Ar rations of 1225 to 3930, indicating that the ore-forming fluids were dominantly derived from crustal sources almost no mantle input. Sulfur isotopic values of Maoling fine-grained granite range from 6.‰1 to 9.8‰, with a mean of 7.7‰, δ³⁴S values of arsenopyrite from the mineralized phyllite (host rock) range from 8.9‰ to 10.6‰, with a mean of 10.0‰, by contrast, δ³⁴S values of sulfides from ore vary between 4.3‰ and 10.6‰, with a mean of 6.8‰, suggesting that sulfur was mainly originated from both the host rock and magma. Lead radioactive isotopic analyses for sulfides yielded ²⁰⁶Pb/²⁰⁴Pb = 15.830–17.103, ²⁰⁷Pb/²⁰⁴Pb = 13.397–15.548, ²⁰⁸Pb/²⁰⁴Pb = 35.478–36.683, and for Maoling fine-grained granite yielded ²⁰⁶Pb/²⁰⁴Pb = 18.757–19.053, ²⁰⁷Pb/²⁰⁴Pb = 15.596–15.612, and ²⁰⁸Pb/²⁰⁴Pb = 38.184–39.309, also suggesting that the ore-forming materials were mainly originated from the host rocks and magma. Zircon U-Pb dating demonstrates that the Maoling fine-grained granite was emplaced at 192.7 ± 1.8 Ma, and the host rock (mineralized phyllite) was emplaced at some time after 2065.0 ± 27.0 Ma. Arsenopyrite and pyrrhotite give Rb–Sr isochron age of 188.7 ± 4.5 Ma, indicating that both magmatism and mineralization occurred during the Early Jurassic. Geochronological and geochemical data, together with the regional geological history, indicate that Early Jurassic magmatism and mineralization of the Maoling gold deposit occurred during the subducting Paleo-Pacific Plate beneath Eurasia, and the Maoling gold deposit is of the intrusion-related gold deposit type.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.     

SA01 – A Proposed Zircon Reference Material for Microbeam U‐Pb Age and Hf‐O Isotopic Determination

A new natural zircon reference material SA01 is introduced for U‐Pb geochronology as well as O and Hf isotope geochemistry by microbeam techniques. The zircon megacryst is homogeneous with respect to U‐Pb, O and Hf isotopes based on a large number of measurements by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS). Chemical abrasion isotope dilution thermal ionisation mass spectrometry (CA‐ID‐TIMS) U‐Pb isotopic analyses produced a mean ²⁰⁶Pb/²³⁸U age of 535.08 ± 0.32 Ma (2s, n = 10). Results of SIMS and LA‐ICP‐MS analyses on individual shards are consistent with the TIMS ages within uncertainty. The δ¹⁸O value determined by laser fluorination is 6.16 ± 0.26‰ (2s, n = 14), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by solution MC‐ICP‐MS is 0.282293 ± 0.000007 (2s, n = 30), which are in good agreement with the statistical mean of microbeam analyses. The megacryst is characterised by significant localised variations in Th/U ratio (0.328–4.269) and Li isotopic ratio (?5.5 to +7.9‰); the latter makes it unsuitable as a lithium isotope reference material.     

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the ²⁰⁴Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (?1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (∼1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the ²⁰⁷Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

Pb isotopic constraints on the formation of the Dikulushi Cu–Pb–Zn–Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

Base metal–Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu–Pb–Zn–Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E–W- and NE–SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.07–18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE–SW-oriented faults into a chalcocite-dominated Cu–Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram (²⁰⁶Pb/²⁰⁴Pb = 18.66–23.65; ²⁰⁷Pb/²⁰⁴Pb = 15.72–16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U–Th–Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu–Pb–Zn–Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the ²⁰⁸Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu–Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.     

Geochemical and petrological aspects of dike intrusions in the Lycian ophiolites (SW Turkey): a case study for the dike emplacement along the Tauride Belt Ophiolites

Lycian ophiolites located in the Western Taurides, are cut at all structural levels by dolerite and gabbro dikes. The dolerite dikes from this area are both pristine and metamorphosed. The non-metamorphosed dikes are observed both in the peridotites and in the metamorphic sole rocks. Accordingly, the non-metamorphosed dikes cutting the metamorphic sole were generated after cooling of the metamorphic sole rocks. The metamorphosed dolerite dikes are only observed in the peridotites. The physical conditions and timing of the metamorphism for the metamorphosed dolerite dikes are similar to those of the metamorphic sole rocks of the Lycian ophiolites suggesting that the metamorphosed dolerite dikes were metamorphosed together with the metamorphic sole rocks. Therefore, the dike injections in the western part of the Tauride Belt Ophiolites occurred before and after the generation of the metamorphic sole rocks. All metamorphosed and non-metamorphosed dikes are considered to have the same origin and all of them are subduction-related as inferred from whole-rock geochemistry and lead isotopes. Lead isotope compositions of whole rocks of both dike groups cluster in a narrow field in conventional Pb isotope diagrams (²⁰⁶Pb/²⁰⁴Pb = 18.40–18.64; ²⁰⁷Pb/²⁰⁴Pb = 15.56–15.58; ²⁰⁸Pb/²⁰⁴Pb = 38.23–38.56) indicating a derivation from an isotopically homogeneous source. On the ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram, isotope compositions of the dikes plot slightly below the orogen curve suggesting contributions from mantle reservoir enriched by subducted oceanic lithosphere. Such a signature is typical of island arc magmatic rocks and supports the formation of the investigated rocks in a subduction-related environment.     

Metal sources of the large Nezhdaninsky orogenic gold deposit, Yakutia, Russia: Results of high-precision MC-ICP-MS analysis of lead isotopic composition supplemented by data on strontium isotopes

A collection of galena from the Nezhdaninsky gold deposit (62 samples), as well as galena from the Menkeche silver-base-metal deposit and the Sentyabr occurrence and K-feldspar from intrusive rocks of the Tyry-Dyby ore cluster have been studied using the high-precision (±0.02%) MC-ICP-MS method. Particular ore zones are characterized by relatively narrow variations of isotope ratios (no wider than σ_6/4 = 0.26%). Vertical zoning of Pb isotopic composition is not detected. Variation in Pb isotope ratios mainly depends on the type of mineral assemblage. Galena of the gold-sulfide assemblage dominating at the Nezhdaninsky deposit is characterized by the following average isotope ratios: ²⁰⁶Pb/²⁰⁴Pb = 18.472, ²⁰⁷Pb/²⁰⁴Pb = 15.586, and ²⁰⁸Pb/²⁰⁴Pb = 38.605. Galena from the regenerated silver-base-metal assemblage is distinguished by less radiogenic lead isotope ratios: 18.420, 15.575, and 38.518, respectively. In lead from the Nezhdaninsky deposit, the component, whose source is identified as Permian host terrigenous rocks, is predominant. The data points of isotopic composition of lode lead make up a linear trend within the range of μ₂ = 9.5-9.6. K-feldspar of granitic rocks has less radiogenic and widely varying lead isotopic composition compared to that of galena. The isotopic data on Pb and Sr constrain the contribution of Late Cretaceous granitic rocks as a source of gold mineralization at the Nezhdaninsky deposit. The matter from the Early Cretaceous fluid-generating magma chamber participated in the ore-forming system of the Nezhdaninsky deposit. The existence of such a chamber is confirmed by the occurrence of Early Cretaceous granitoid intrusions on the flanks of the Nezhdaninsky ore field. The greatest contribution of magmatic lead (～30%) is noted in galena from the silver-base-metal mineral assemblage. This component has isotopic marks characteristic of lower crustal lead: the elevated ²⁰⁸Pb/²⁰⁶Pb ratio relative to the mean crustal value and the lower ²⁰⁷Pb/²⁰⁴Pb ratio. Taken together, they determine a high Th/U ～ 4.0 in the source and μ₂ = 9.37–9.50. This conclusion is consistent with the contemporary tectonic model describing evolution of the South Verkhoyansk sector of the Verkhoyansk Foldbelt and the Okhotsk Terrane.     

Lead isotopes of the carbonate-hosted Kabwe, Tsumeb, and Kipushi Pb-Zn-Cu sulphide deposits in relation to Pan African orogenesis in the Damaran-Lufilian Fold Belt of Central Africa

Lead isotope ratios of galena from the carbonate-hosted massive sulphide deposits of Kabwe (Pb-Zn) and Tsumeb (Pb-Zn-Cu) in Zambia and Namibia, respectively, have been measured and found to be homogeneous and characteristic of upper crustal source rocks. Kabwe galena has average isotope ratios of ^206/204Pb = 17.997 ± 0.007, ^207/204Pb = 15.713 ± 0.010 and ^208/204Pb = 38.410 ± 0.033. Tsumeb galena has slightly higher ^206/204Pb (18.112 ± 0.035) and slightly lower ^207/204Pb (15.674 ± 0.016) and ^208/204Pb (38.276 ± 0.073) ratios than Kabwe galena. The isotopic differences are attributed to local differences in the age and composition of the respective source rocks for Kabwe and Tsumeb. The homogeneity of the ore lead in the two epigenetic deposits suggests lead sources of uniform isotopic composition or, alternatively, thorough mixing of lead derived from sources with relatively similar isotopic compositions. Both deposits have relatively high ²³⁸U/²⁰⁴Pb ratios of 10.31 and 10.09 for Kabwe and Tsumeb galenas, respectively. These isotope ratios are considered to be typical of the upper continental crust in the Damaran-Lufilian orogenic belt, as also indicated by basement rocks and Cu-Co sulphides in stratiform Katangan metasediments which have a mean μ-value of 10.25 ± 0.12 in the Copperbelt region of Zambia and the Democratic Republic of Congo (formerly Zaire). The ²³²Th/²⁰⁴Pb isotope ratios of 43.08 and 40.42 for Kabwe and Tsumeb suggest Th-enriched source regions with ²³²Th/²³⁵U (κ-values) of 4.18 and 4.01, respectively. Model isotopic ages determined for the Kabwe (680 Ma) and Tsumeb (530 Ma) deposits indicate that the timing of the mineralisation was probably related to phases of orogenic activity associated with the Pan-African Lufilian and Damaran orogenies, respectively. Galena from the carbonate-hosted Kipushi Cu-Pb-Zn massive sulphide deposit in the Congo also has homogeneous lead isotope ratios, but its isotopic composition is comparable to that of the average global lead evolution curve for conformable massive sulphide deposits. The μ (9.84) and κ (3.69) values indicate a significant mantle component, and the isotopic age of the Kipushi deposit (456 Ma) suggests that the emplacement of the mineralisation was related to a post-tectonic phase of igneous activity in the Lufilian belt. The isotope ratios (^206/204Pb, ^207/204Pb, ^208/204Pb) of the three deposits are markedly different from the heterogeneous lead ratios of the Katangan Cu-Co stratiform mineralisation of the Copperbelt as well as those of the volcanogenic Nampundwe massive pyrite deposit in the Zambezi belt which typically define radiogenic linear trends on lead-lead plots. The host-rock dolomite of the Kabwe deposit also has homogeneous lead isotope ratios identical to the ore galena. This observation indicates contamination of the Kabwe Dolomite Formation with ore lead during mineralisation. Received: 8 September 1997 / Accepted: 21 August 1998     

Source components of the Gran Canaria (Canary Islands) shield stage magmas: evidence from olivine composition and Sr–Nd–Pb isotopes

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6–90.0 mol.% Fo, 1,722–3,915 ppm Ni, 1,085–1,552 ppm Mn, 1,222–3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr–Nd–Pb isotope compositions (⁸⁷Sr/⁸⁶Sr = 0.70315–0.70331, ¹⁴³Nd/¹⁴⁴Nd = 0.51288–0.51292, ²⁰⁶Pb/²⁰⁴Pb = 19.55–19.93, ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.63, ²⁰⁸Pb/²⁰⁴Pb = 39.31–39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al. in: Science 316:412–417, 2007) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with ⁸⁷Sr/⁸⁶Sr = 0.70337, ¹⁴³Nd/¹⁴⁴Nd = 0.51291, ²⁰⁶Pb/²⁰⁴Pb = 19.36, ²⁰⁷Pb/²⁰⁴Pb = 15.61 and ²⁰⁸Pb/²⁰⁴Pb = 39.07 (EM-type end member), and pyroxenite with ⁸⁷Sr/⁸⁶Sr = 0.70309, ¹⁴³Nd/¹⁴⁴Nd = 0.51289, ²⁰⁶Pb/²⁰⁴Pb = 20.03, ²⁰⁷Pb/²⁰⁴Pb = 15.62 and ²⁰⁸Pb/²⁰⁴Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al. EPSL 277:514–524, 2009), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.     

Metamorphism, isotopic ages and composition of lower crustal granulite xenoliths from the Cretaceous Salta Rift, Argentina

Crustal xenoliths from basanitic dikes and necks that intruded into continental sediments of the Cretaceous Salta Rift at Quebrada de Las Conchas, Provincia Salta, Argentina were investigated to get information about the age and the chemical composition of the lower crust. Most of the xenoliths have a granitoid composition with quartz-plagioclase-garnet-rutile ± K-feldspar as major minerals. The exceedingly rare mafic xenoliths consist of plagioclase-clinopyroxene-garnet ± hornblende. All xenoliths show a well equilibrated granoblastic fabric and the minerals are compositionally unzoned. Thermobarometric calculations indicate equilibration of the mafic xenoliths in the granulite facies at temperatures of ca. 900 °C and pressures of ca. 10 kbar. The Sm-Nd mineral isochron ages are 95.1 ± 10.4 Ma, 91.5 ± 13.0 Ma, 89.0 ± 4.2 Ma (granitoid xenoliths), and 110.7 ± 23.6 Ma (mafic xenolith). These ages are in agreement with the age of basanitic volcanism (ca. 130–100 and 80–75 Ma) and are interpreted as minimum ages of metamorphism. Lower crustal temperature at the time given by the isochrons was above the closure temperature of the Sm-Nd system (>600–700 °C). The Sm-Nd and Rb-Sr isotopic signatures (¹⁴⁷Sm/¹⁴⁴Nd = 0.1225–0.1608; ¹⁴³Nd/¹⁴⁴Nd_{t 0} = 0.512000–0.512324; ⁸⁷Rb/⁸⁶Sr = 0.099–0.172; ⁸⁷Sr/⁸⁶Sr_{t 0} = 0.708188–0.7143161) and common lead isotopic signatures (²⁰⁶Pb/²⁰⁴Pb = 18.43–18.48; ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.70; ²⁰⁸Pb/²⁰⁴Pb = 38.22 –38.97) of the granitoid xenoliths are indistinguishable from the isotopic composition of the Early Paleozoic metamorphic basement from NW Argentina, apart from the lower ²⁰⁸Pb/²⁰⁴Pb ratio of the basement. The Sm-Nd depleted mantle model ages of ca. 1.8 Ga from granitoid xenoliths and Early Paleozoic basement point to a similar Proterozoic protolith. Time constraints, the well equilibrated granulite fabric, P-T conditions and lack of chemical zoning of minerals point to a high temperature in a crust of nearly normal thickness at ca. 90 Ma and to a prominent thermal anomaly in the lithosphere. The composition of the xenoliths is similar to the composition of the Early Paleozoic basement in the Andes of NW Argentina and northern Chile. A thick mafic lower crust seems unlikely considering low abundance of mafic xenoliths and the predominance of granitoid xenoliths. Received: 21 July 1998 / Accepted: 27 October 1998     

Geochronology and geochemistry of volcanic rocks of the Bima Formation,southern Lhasa subterrane,Tibet: Implications for early Neo-Tethyan subduction

Bima Formation volcanic rocks, which record the history of Neo-Tethyan subduction, are found within the central and eastern segments of the southern Lhasa subterrane, Tibetan Plateau. Zircon UPb dating, whole-rock major and trace element analysis, and Sr–Nd–Pb–Hf isotopic compositions of Bima Formation volcanic rocks from the central segment of the southern Lhasa subterrane were used to constrain the magmatic and tectonic evolution of the Lhasa terrane during the early Mesozoic. Zircon UPb dating of five samples yielded consistent ages of 184.3 ± 2.4 to 176.8 ± 3.5 Ma. The dominant volcanic rock types within the Bima Formation are basalts, basaltic andesites, andesites, and dacites, which are enriched in the large-ion lithophile elements (e.g., Rb, Sr, and Ba) and depleted in high-field-strength elements (e.g., Nb, Ta, and Ti). (⁸⁷Sr/⁸⁶Sr)_t ratios are low (0.702900–0.704146), ε_Nd(t) and ε_Hf(t) values are high and positive (+4.4 to +6.9 and + 9.6 to +15.7, respectively), and Pb isotope ratios are homogeneous (initial ²⁰⁶Pb/²⁰⁴Pb = 18.28–18.40; ²⁰⁷Pb/²⁰⁴Pb = 15.53–15.56; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.38). Combining the new data with those from a previous study of Bima Formation volcanic rocks from the eastern segment of the southern Lhasa subterrane indicates that the Bima Formation formed between the Middle Triassic and Early Jurassic. It suggests that more widespread early Mesozoic volcanic rocks in the southern margin of the Lhasa terrane. The basaltic rocks of the Bima Formation were generated by partial melting of a depleted mantle wedge metasomatized by slab-derived fluids, and subsequently experienced fractional crystallization without significant crustal contamination. The andesitic and dacitic rocks were formed by fractional crystallization of the basaltic magma. Our study indicates that the Bima Formation volcanic rocks were generated within a continental island arc setting related to northward subduction of the Neo-Tethyan oceanic slab during the early Mesozoic.     

Characterisation of Three Sri Lankan Zircon Megacrysts as Potential Reference Materials for Microbeam U-Pb Geochronology and Hf-O-Zr Isotope Measurements

In situ U-Pb geochronology and hafnium, oxygen and zirconium isotope measurements in zircons using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and ion microprobe techniques can provide essential isotopic data to constrain geological evolutionary histories. Developing reliable zircon reference materials is the cornerstone for in situ zircon chronology and isotopic studies. In this study, the homogeneity of U-Pb ages and Hf-O-Zr isotope ratios in three Sri Lankan zircon megacrysts (SLZA, SLZB and SLZC) were investigated using multiple analytical methods. The obtained U, Th, Pb and Hf mass fractions of the SLZA zircon were 839 ± 56 μg g^-1 (1s), 151 ± 15 μg g^-1 (1s), 198 ± 28 μg g^-1 (1s) and 8635 ± 286 μg g^-1 (1s), respectively. The mass fractions of U, Th, Pb and Hf in the SLZB zircon were 1106 ± 106 μg g^-1 (1s), 331 ± 61 μg g^-1 (1s), 376 ± 57 μg g^-1 (1s) and 9673 ± 976 μg g^-1 (1s), respectively. The U, Th, Pb and Hf mass fractions determined in the SLZC zircon were 551 ± 35 μg g^-1 (1s), 111 ± 8 μg g^-1 (1s), 129 ± 18 μg g^-1 (1s) and 7881 ± 393 μg g^-1 (1s), respectively. The chemical abrasion isotope dilution thermal ionisation mass-spectrometry (CA-ID-TIMS) method yielded a Th-corrected weighted mean ²⁰⁶Pb/²³⁸U age of 556.94 ± 1.29 Ma (95% conf., n = 5) for the SLZA zircon, 552.90 ± 1.29 Ma (95% conf., n = 7) for the SLZB zircon and 560.83 ± 1.29 Ma (95% conf., n = 7) for the SLZC zircon. The obtained Hf isotopic compositions of the SLZA, SLZB and SLZC zircons determined with the solution MC-ICP-MS method were 0.281651 ± 0.000014 (2s, n = 10), 0.281704 ± 0.000008 (2s, n = 10) and 0.281676 ± 0.000006 (2s, n = 10), respectively. The obtained O isotopes of the SLZA and SLZB zircons measured with the laser fluorination method were 12.14 ± 0.56‰ (2s, n = 4) and 11.91 ± 0.30‰ (2s, n = 4), respectively. The Zr isotopes of the SLZA, SLZB and SLZC zircons determined with double spike TIMS analysis yielded mean δ⁹⁴/⁹⁰Zr_SRM3169 values of -0.03 ± 0.06‰ (2s, n = 10), -0.03 ± 0.04‰ (2s, n = 10) and 0.00 ± 0.07‰ (2s, n = 8), respectively. The SLZA zircon can be used as a primary reference or quality control material for microbeam U-Pb, Hf and Zr isotope measurements because of its slight heterogeneity. The U-Pb, Hf and Zr isotopic compositions of the SLZB and SLZC megacrysts were homogeneous. The O isotopic compositions in the SLZA and SLZB zircon were slightly dispersed, indicating that these two megacrysts can only serve as secondary reference materials for microbeam O isotope measurements.     

Origin of the Maoduan Pb–Zn–Mo deposit, eastern Cathaysia Block, China: geological, geochronological, geochemical, and Sr–Nd–Pb–S isotopic constraints

The Maoduan Pb–Zn–Mo deposit is in hydrothermal veins with a pyrrhotite stage followed by a molybdenite and base metal stage. The Re–Os model ages of five molybdenite samples range from 138.6 ± 2.0 to 140.0 ± 1.9 Ma. Their isochron age is 137.7 ± 2.7 Ma. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb dating of the nearby exposed Linggen granite porphyry gave a ²⁰⁶Pb/²³⁸U age of 152.2 ± 2.2 Ma and the hidden Maoduan monzogranite yielded a mean of 140.0 ± 1.6 Ma. These results suggest that the intrusion of the Maoduan monzogranite and Pb–Zn–Mo mineralization are contemporaneous. δ ³⁴S values of sulfide minerals range from 3.4‰ to 4.8‰, similar to magmatic sulfur. Four sulfide samples have ²⁰⁶Pb/²⁰⁴Pb = 18.252–18.432, ²⁰⁷Pb/²⁰⁴Pb = 15.609–15.779, and ²⁰⁸Pb/²⁰⁴Pb = 38.640–39.431, similar to the age-corrected data of the Maoduan monzogranite. These isotope data support a genetic relationship between the Pb–Zn–Mo mineralization and the Maoduan monzogranite and probably indicate a common deep source. The Maoduan monzogranite has geochemical features similar to highly fractionated I-type granites, such as high SiO₂ (73.7–75.2 wt.%) and alkalis (K₂O + Na₂O = 7.8–8.9 wt.%) and low FeO_t (0.8–1.3 wt.%), MgO (~0.3 wt.%), P₂O₅ (~0.03 wt.%), and TiO₂ (~0.2 wt.%). The granitic rocks are enriched in Rb, Th, and U but depleted in Ba, Sr, Nb, Ta, P, and Ti. REE patterns are characterized by marked negative Eu anomalies (Eu/Eu^* = 0.2–0.4). The Maoduan monzogranite, having (⁸⁷Sr/⁸⁶Sr) _t  = 0.7169 to 0.7170 and ε_Nd(t) = −13.8 to −13.7, was probably derived from mixing of partial melts from enriched mantle and the Paleoproterozoic Badu group in an extensional tectonic setting.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected ²⁰⁶Pb/²³⁸U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam ²⁰⁶Pb/²³⁸U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf₀ of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of ²⁰⁶Pb/²³⁸U and ¹⁷⁶Hf/¹⁷⁷Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic ¹⁷⁶Hf/¹⁷⁷Hf.     

Petrogenesis of the Neogene volcanic units in the NE–SW-trending basins in western Anatolia,Turkey

The western Anatolian volcanic province formed during Eocene to Recent times is one of the major volcanic belts in the Aegean–western Anatolian region. We present new chemical (whole-rock major and trace elements, and Sr, Nd, Pb and O isotopes) and new Ar/Ar age data from the Miocene volcanic rocks in the NE–SW-trending Neogene basins that formed on the northern part of the Menderes Massif during its exhumation as a core complex. The early-middle Miocene volcanic rocks are classified as high-K calc-alkaline (HKVR), shoshonitic (SHVR) and ultrapotassic (UKVR), with the Late Miocene basalts being transitional between the early-middle Miocene volcanics and the Na-alkaline Quaternary Kula volcanics (QKV). The early-middle Miocene volcanic rocks are strongly enriched in large ion lithophile elements (LILE), have high ⁸⁷Sr/⁸⁶Sr_(i) (0.70631–0.71001), low ¹⁴³Nd/¹⁴⁴Nd_(i) (0.512145–0.512488) and high Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb = 18.838–19.148; ²⁰⁷Pb/²⁰⁴Pb = 15.672–15.725; ²⁰⁸Pb/²⁰⁴Pb = 38.904–39.172). The high field strength element (HFSE) ratios of the most primitive early-middle Miocene volcanic rocks indicate that they were derived from a mantle source with a primitive mantle (PM)-like composition. The HFSE ratios of the late Miocene basalts and QKV, on the other hand, indicate an OIB-like mantle origin—a hypothesis that is supported by their trace element patterns and isotopic compositions. The HFSE ratios of the early-middle Miocene volcanic rocks also indicate that their mantle source was distinct from those of the Eocene volcanic rocks located further north, and of the other volcanic provinces in the region. The mantle source of the SHVR and UKVR was influenced by (1) trace element and isotopic enrichment by subduction-related metasomatic events and (2) trace element enrichment by “multi-stage melting and melt percolation” processes in the lithospheric mantle. The contemporaneous SHVR and UKVR show little effect of upper crustal contamination. Trace element ratios of the HKVR indicate that they were derived mainly from lower continental crustal melts which then mixed with mantle-derived lavas (~20–40%). The HKVR then underwent differentiation from andesites to rhyolites via nearly pure fractional crystallization processes in the upper crust, such that have undergone a two-stage petrogenetic evolution.     

Fluid evolution and ore genesis of the A'gui Cu deposit in southern Great Xing'an Range,Northeast China: Evidence from fluid inclusion and C–H–O–S–Pb isotopes

The A'gui Cu deposit is located in the eastern slope of the southern Great Xing'an Range (SGXR), and it is a vein-type Cu deposit spatially and temporally related to the Cretaceous monzogranite which intruded Pingshan Formation. Vein-type Cu orebodies are mainly hosted in the NE and nearly EW faults. Previous studies on the A'gui deposit mainly focused on geological exploration, and there was no study on its fluid evolution and genesis. Therefore, we carried out conducted fluid inclusion and stable isotope (C–H–O–S–Pb) analysis to study the fluid evolution, fluid and ore-forming material sources and genesis of the A'gui deposit. According to the field investigations and mineral crosscutting relationships, four paragenetic stages were identified: quartz–pyrite–chalcopyrite–pyrrhotite–arsenopyrite ± magnetite (Stage I), quartz–pyrite–chalcopyrite (Stage II), quartz–chalcopyrite ± pyrite–sphalerite–galena (Stage III) and carbonate ± quartz (Stage IV). From Stage I to Stage II, the assemblage of fluid inclusions (FIs) in quartz is characterized by the development of daughter mineral–bearing three–phase FIs (SL–type), vapour FIs (V–type), vapour–rich two–phase aqueous FIs (LV–type) and liquid–rich two–phase aqueous FIs (VL–type). Only VL–type FIs appeared in the Stage III quartz and Stage IV calcite. The homogenization temperatures of FIs in stages I, II, III and IV are 329–390 °C, 255–336 °C, 166–244 °C and 120–157 °C, with salinities of 3.37–45.33 wt%, 3.53–39.76 wt%, 4.17–7.86 wt% and 3.37–7.15 wt% NaCl eqv., respectively. The fluid inclusion type assemblage suggested that obvious fluid boiling occurred in the Stage I and Stage II. Fluid boiling may be the reason for the precipitation of useful minerals. According to the HO isotope analysis of stages I–II quartz (δ¹⁸O_H2O = −2.1 to 3.2 ‰, δD_V–SMOW = −128.4 ‰ to −110.6 ‰), the fluid was originally magmatic water. From Stage III to Stage IV (δ¹⁸O_H2O = −12.3 to −2.3 ‰, δD_V–SMOW = −129.6 ‰ to −104.2 ‰), the HO isotope value is obviously close to the meteoric water line, indicating that meteoric water is mixed with evolved magmatic solutions. The ore–forming fluid of the A'gui deposit represents a medium–high temperature NaCl-H₂O magmatic hydrothermal system. The C isotope compositions (δC_V–PDB = −5.74 ‰ to −4.76 ‰) in stage IV indicate that the C in the fluid was derived from a magmatic source and was affected by meteoric water. In addition, the measured S isotope compositions in stages I–III of the hydrothermal fluids (δ³⁴S_V–CDT = 2.2 to 3.7 ‰) indicate that S mainly comes from granitic magma. Further, the Pb isotope (²⁰⁶Pb/²⁰⁴Pb = 18.276–18.367, ²⁰⁷Pb/²⁰⁴Pb = 15.52–15.556, ²⁰⁸Pb/²⁰⁴Pb = 38.157–38.193) in stages I–III indicate that the ore-forming materials are derived from the mixture of mantle and orogenic material. In summary, this study showed the A'gui is a typical magmatic hydrothermal vein-type Cu deposit that related to Cretaceous monzogranite formed under the joint constraints of Mongolia-Okhotsk Ocean and Paleo-Pacific Ocean tectonic system. Fluid boiling and mixing are the main ore-forming mechanism.     

High-precision Pb isotope analysis by multicollector-ICP-mass-spectrometry using 205Tl/203Tl normalization: Optimization and calibration of the method for the studies of Pb isotope variations

The development of the MC-ICP-MS method, which was launched about one decade ago and was largely stimulated by the need to solve geological problems, has opened a new avenue in isotope mass spectrometry. One of the advantages of this method is the possibility of applying a newly developed approach to the correction of analytical results for the effect of mass discrimination by normalizing the measured isotope ratios of an element to a reference (standard) isotope ratio of another element. This makes it possible to overcome the main disadvantage of conventional thermal ionization mass spectrometry (TIMS), in which the effect of mass discrimination cannot be fully taken into account during isotope analysis, and thus to implement a highly accurate method for the analysis of Pb-isotope composition. In application to the capability of the NEPTUNE MC-ICP mass spectrometer, we optimized and calibrated a method for high-accuracy Pb isotope analysis in solutions spiked with Tl, with all currently measured Pb-isotope ratios normalized to the standard ²⁰⁵Tl/²⁰³Tl ratio (TLN-MC-ICP-MS). The factors affecting the random and systematic analytical errors were examined, and the optimal operating regime and analytical conditions were determined. Much attention was paid to the correlation of the measurement results and the mass discrimination effect determined from the ²⁰⁵Tl/²⁰³Tl ratio. The value of the ²⁰⁵Tl/²⁰³Tl normalizing ratio was analytically determined through isotope analyses of the NIST SRM 981, and SRM 982 standard samples of Pb-isotope composition. The data obtained for two mixtures Tl + Pb (SRM 982) and Tl + Pb (SRM 981) in ten replicate analyses were 2.38898 ± 12 and 2.38883 ± 20, respectively. These results are in good mutual agreement, and their general mean ²⁰⁵Tl/²⁰³Tl = 2.3889 ± 1 coincides (within the error) with the recently published values of 2.3887 ± 7 [Collerson et al., 2002] and 2.3889 ± 1 [Thirlwall, 2002]. The precision of the method (±2SD), which was assayed by the long-term reproducibility of the results of replicate analyses of SRM 981 and seven galena samples (90 analyses) was 0.016–0.018% for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios and 0.005 and 0.009% for the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios, respectively. The precision of the isotope analysis of common Pb was significantly improved (by factors of 6–10 for various isotope ratios) compared with the precision of TIMS techniques acceptable in isotope studies during three decades. The described method was applied to examine the Pb-isotope composition of approximately 250 samples of galena, scheelite, and pyrite from a number of well known (including large) gold, sulfied, and base-metal deposits. The precision of the method (0.01–0.02%) makes it possible to study small inter-and intra-phase differences in Pb-isotope ratios in hydrothermal and magmatic rocks, to assay the scale of regional and variations in the isotope composition of ore Pb, and to correlate the Pb-isotope composition of rocks and ores and reveal its evolutionary trends.