MC-ICP-MS高精度测定Pb同位素比值

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一，通过用等离子体质谱测量Pb国际标准物质NBS981和NBS982,显示出多接收器等离子体质谱分析Pb同位素的优势。利用205Tl/203Tl进行作为内标，可以实现Pb同位素的质量分馏校正，极大地提高了Pb同位素分析的重现性。相比较热电离质谱，该方法精度更高，样品的用量更少，测试时间更短，多接收器等离子体质谱测定Pb同位素技术有良好的应用前景。     

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock reference standards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BER-1/1 and W-2, together with NBS 981 using a micromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at the University of Queensland. 203Tl-205Tl isotopes were used as an internal standard to correct for mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standards AGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionization mass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2 are reproducibly higher for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb than double-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR-1/1 and W-2, which may be used as reference values in future studies. It is found that linear correction for Pb isotopic fractionation is adequate with the results identical to those corre     

Lead Isotope Homogeneity of NIST SRM 610 and 612 Glass Reference Materials: Constraints from Laser Ablation Multicollector ICP-MS (LA-MC-ICP-MS) Analysis

This contribution presents data for laser ablation multicollector ICP‐MS (LA‐MC‐ICP‐MS) analyses of NIST SRM 610 and 612 glasses with the express purpose of examining the Pb isotope homogeneity of these glasses at the ～ 100 μm spatial scale, relevant to in situ analysis. Investigation of homogeneity at these scales is important as these glasses are widely used as calibrators for in situ measurements of Pb isotope composition. Results showed that at the levels of analytical uncertainty obtained, there was no discernable heterogeneity in Pb isotope composition of NIST SRM 610 and also most probably for NIST SRM 612. Traverses across the ～ 1.5 mm glass wafers supplied by NIST, consisting of between 75 and 133 individual measurements, showed no compositional outliers at the two standard deviation level beyond those expected from population statistics. Overall, the measured Pb isotope ratios from individual traverses across NIST SRM 610 and 612 wafers closely approximate single normally‐distributed populations, with standard deviations similar to the average internal uncertainty for individual measurement blocks. Further, Pb isotope ratios do not correlate with Tl/Pb ratios measured during the analysis, suggesting that regions of volatile element depletion (marked by low Tl/Pb) in these glasses are not associated with changes in Pb isotope composition. For NIST SRM 610 there also appeared to be no variation in Pb isotope composition related to incomplete mixing of glass base and trace element spike during manufacture. For NIST SRM 612 there was some dispersion of measured ratios, including some in a direction parallel to the expected mixing line for base‐spike mixing. However, there was no significant correlation parallel to the mixing line. At this time this cannot be unequivocally demonstrated to result from glass heterogeneity, but it is suggested that NIST SRM 610 be preferred for standardising in situ Pb isotope measurements. Data from this study also showed significantly better accuracy and somewhat better precision for ratios corrected for mass bias by external normalisation to Pb isotope ratios measured in bracketing calibrators compared to mass bias corrected via internal normalisation to measured ²⁰⁵Tl/²⁰³Tl, although the Tl isotopic composition of both glasses appears to be homogeneous.     

Large thallium isotopic variations in iron meteorites and evidence for lead-205 in the early solar system

Lead-205 decays to ²⁰⁵Tl with a half-life of 15 Myr and should have been present in the early solar system according to astrophysical models. However, despite numerous attempts, Tl isotopic measurements of meteorites have been unable to demonstrate convincingly its former presence. Here, we report large (∼5‰) variations in Tl isotope composition in metal and troilite fragments from a range of iron meteorites that were determined at high precision using multiple collector inductively coupled plasma mass spectrometry. The Tl isotopic compositions of seven metal samples of the IAB iron meteorites Toluca and Canyon Diablo define a correlation with ²⁰⁴Pb/²⁰³Tl. When interpreted as an isochron, this corresponds to an initial ²⁰⁵Pb/²⁰⁴Pb ratio of (7.4 ± 1.0) × 10⁻⁵. Alternative explanations for the correlation, such as mixing of variably mass-fractionated meteorite components or terrestrial contamination are harder to reconcile with independent constraints. However, troilite nodules from Toluca and Canyon Diablo contain Tl that is significantly less radiogenic than co-existing metal with isotope compositions that are variable and decoupled from ²⁰⁴Pb/²⁰³Tl. These effects are similar to those recently reported by others for Fe and Ni isotopes in iron meteorite sulfides and appear to be the result of kinetic stable isotope fractionation during diffusion. Though it cannot conclusively be shown that the metal fragments are unaffected by the secondary processes that disturbed the troilites, mass balance modeling indicates that the alteration of the troilites is unlikely to have significantly affected the Tl isotope compositions of the co-existing metals. It is therefore reasonable to conclude that the IAB metal isochron is a product of the in situ decay of ²⁰⁵Pb. If the I-Xe ages of IAB silicate inclusions record the same event as the ²⁰⁵Pb-²⁰⁵Tl chronometer then crystallization of the IAB metal was probably completed between 10 and 20 Myr after the condensation of the first solids. This implies an initial solar system ²⁰⁵Pb/²⁰⁴Pb of (1.0-2.1) × 10⁻⁴, which is in excellent agreement with recently published astrophysical predictions. Similar calculations yield an initial solar system Tl isotope composition of ε²⁰⁵Tl = −2.8 ± 1.7. The Tl isotopic composition and concentration of the silicate Earth depends critically on the timing and mechanism of core formation and Earth’s volatile element depletion history. Modeling of the Earth’s accretion and core formation using the calculated initial solar system Tl isotope composition and ²⁰⁵Pb/²⁰⁴Pb, however, does not yield reasonable results for the silicate Earth unless either the Earth lost Tl and Pb late in its accretion history or the core contains much higher concentrations of Pb and Tl than are found in iron meteorites.     

Lead Isotope composition and origin of the quaternary lavas of Elbrus Volcano, the Greater Caucasus: High-precision MC-ICP-MS data

A systematic study of Pb isotope composition was carried out for Elbrus Volcano, one of the Europe’s largest volcanoes, using high-precision method of multi-collector inductively coupled plasma mass spectrometry. The measurement error of Pb isotope ratios was estimated from the results of replicate analyses of international BCR-1 and AGV-1 standards as ±0.03% (±2SD). The study of a representative collection showed that dacites of all three phases of the Elbrus eruptive activity are characterized by relatively small-scale variations of Pb isotope composition: ²⁰⁶Pb/²⁰⁴Pb 18.621–18.670, ²⁰⁷Pb/²⁰⁴Pb 15.636–15.659, and ²⁰⁸Pb/²⁰⁴Pb 38.762–38.845. New Pb isotope geochemical characteristics in combination with existing Sr-Nd data indicate that the parental magmas of Elbrus are of mixed mantle-crust origin. They were formed by interaction of mantle-derived melts with continental crust of the Greater Caucasus during continental collision between the Eurasian, Arabian, Turkish, and Iranian plates.     

Thallium isotope composition of the upper continental crust and rivers—An investigation of the continental sources of dissolved marine thallium

The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols.The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ε²⁰⁵Tl = −2.0 ± 0.3 (ε²⁰⁵Tl represents the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 10⁴). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ±1.5 ε²⁰⁵Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ± 4 ng/kg and ε²⁰⁵Tl = −2.5 ± 1.0, respectively.In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study.     

Lead isotope signatures of Pb-Zn sulfide mineralization in the Reshian-Lamnian area of Azad Jammu and Kashmir,Pakistan

The Reshian-Lamnian area within the Hazara-Kashmir syntaxis in Pakistan is composed mainly of the rocks of the Salkhala, Panjal and Murree formations. Base metal sulfide mineralization in the form of sphalerite and galena with lesser amounts of chalcopyrite and pyrite is present within the Salkhala Formation of the study area. Chemically all these ore phases are homogeneous in composition. The Pb isotopic composition of galena from the area suggests that there is very little or negligible variation in the ratios of ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb. Modal ages ranging from 509 to 562 Ma and the μ values of 10.71 to 10.93 have been calculated for the studied Pb-Zn mineralization. On the basis of field features, mineralogy and Pb-isotope signatures, it is concluded that the Pb-Zn sulfide mineralization in the Reshian-Lamnia area is pre-Himalayan in age and can be correlated with the Cambro-Ordovician (Pan-African) orogenic event.     

Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl-Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε²⁰⁵Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε²⁰⁵Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε²⁰⁵Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε²⁰⁵Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.     

Lead isotopic composition from data of high-precession MC-ICP-MS and sources of matter in the large-scale Sukhoi Log noble metal deposit,Russia

The lead isotopic composition of 33 sulfide samples from orebodies of the Sukhoi Log deposit was studied by high-precession MC-ICP-MS with a precision of ±0.02% (±2SD from 120 analyses of the SRM 981 standard sample). The deposit is located in the Bodaibo gold mining district in the northern Baikal-Patom Highland. Gold mineralization is hosted in Neoproterosoic black slates. Variations of lead isotope ratios of the Sukhoi Log sulfides are generally typical of Phanerozoic deposits and ore fields. They are significant for ²⁰⁶Pb/²⁰⁴Pb (17.903–18.674), moderate for ²⁰⁸Pb/²⁰⁴Pb (37.822–38.457), and relatively narrow for ²⁰⁷Pb/²⁰⁴Pb (15.555–15.679). In the Pb-Pb isotope diagrams, the data points of pyrite and galena constitute a linear trend. The points corresponding to pyrite from metasomatic ore occupy the left lower part of the trend. Galena from late gold-quartz veins shows more radiogenic Pb, and corresponding data points are located in the upper part of the trend. According to the Stacey-Kramers model, the end points of the trend, which is regarded as a mixing line, have μ₂ = 9.6 and μ₂ = 13.2 and model Pb-Pb ages 455 and 130 Ma, respectively. The isotope characteristics of ore lead, their relationships in pyrite and galena, and the mixing trend of Pb isotopic compositions are clearly tied to two Paleozoic stages in the formation of the Sukhoi Log deposit (447 ± 6 and 321 ± 14Ma) and testify to the leading role of crustal sources, which are suggested as being the Neoproterozoic black-shale terrigenous-carbonate rocks.     

Lead isotope distribution and enrichment factors in soil profiles around an abandoned Pb-smelter plant

Todos os Santos (all Saints) Bay area on Brazil’s east coast is known for one of the most significant cases of lead contamination in the country owing to the past activities of a Pb-smelter plant. This work was carried out to assess the concentration and sources of Pb based on Pb isotopes and enrichment factor of soil profiles surrounding Todos os Santos Bay in order to understand the expansion of contamination and to help the establishment of Pb regulatory standards for the region. Forty-four samples were collected from soil genetic horizons of six pedons that represent the range of dominant soil properties and geologic materials in the region. Concentrations of Pb and the isotopes ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb were determined on an inductively coupled plasma (quadrupole) mass spectrometry. The soil enrichment factor was calculated using Al and Fe as conservative index elements. Average Pb concentration (15.87 mg kg^?1) in uppermost horizons (from all six pedons) is slightly higher than soil background concentrations commonly reported in Brazil. Samples feature a wide range of Pb isotope ratios, ranging from 36.71 to 47.38 for ²⁰⁸Pb/²⁰⁴Pb, 15.00 to 15.65 for ²⁰⁷Pb/²⁰⁴Pb, 16.86 to 20.59 for ²⁰⁶Pb/²⁰⁴Pb, and 1.10 to 1.31 for ²⁰⁶Pb/²⁰⁷Pb. For the enrichment factor calculations, only Fe demonstrated a good agreement with Pb isotopic ratios. Both Pb isotopic composition and enrichment factor were useful tools to distinguishing natural and anthropogenic influence on the Pb soil concentrations.     

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     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Lead isotope systematics of vein-type antimony mineralization,Rheinisches Schiefergebirge,Germany: a case history of complex reaction and remobilization processes

Mesothermal vein-type Sb mineralization in the Rheinisches Schiefergebirge, Germany, is characterized by two different mineralization styles, which are (1) extensional quartz-stibnite vein systems, and (2) (Cu)-Pb-Sb sulphosalt assemblages in overprinted pre-existing Pb-Zn veins. A detailed Pb isotope study of 52 representative samples from both mineralization types indicates distinct compositional patterns. (Cu)-Pb-Sb sulphosalts (meneghinite, boulangerite, bournonite) formed by reaction/remobilization are characterized by Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb=18.179-18.223), which are identical to the precursor galena (²⁰⁶Pb/²⁰⁴Pb=18.168-18.223). The Pb isotope composition of sulphosalt minerals in these vein systems was controlled by lead inherited from pre-existing galena. Stibnite and Pb-sulphosalts (zinkenite, semseyite, plagionite) formed in quartz-stibnite vein systems display Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb=18.250-18.354), which are more radiogenic than galenas from Variscan Pb-Zn ore veins (²⁰⁶Pb/²⁰⁴Pb=18.162-18.303). Detailed small-scale investigation of thrust zones hosting Pb-Zn ores and crosscutting quartz-ankerite fissure veins (Ramsbeck deposit) indicates that the Pb isotope compositions of recrystallized (galena) and remobilized phases (boulangerite, semseyite, bournonite) are arranged along a linear trend. This is interpreted as mixing between primary galena with ²⁰⁶Pb/²⁰⁴Pb᜞.206 and overprinting hydrothermal fluids with a more radiogenic composition (²⁰⁶Pb/²⁰⁴Pb⁾.354), expressed by intermediate compositions (²⁰⁶Pb/²⁰⁴Pb=18.256-18.334) of newly-formed sulphosalts. The Pb isotope systematics of the vein-type Sb mineralization is in accordance with a model of Pb extraction from similar crustal sources (Palaeozoic sedimentary sequences) at different times.     

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.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.     

Lead isotopic systematics of major river sediments: a new estimate of the Pb isotopic composition of the Upper Continental Crust

The lead isotopic composition of river sediments is reported in the present work for the Earth's major river basins, from old cratonic to young orogenic areas and from subarctic to tropical climates. Sediment samples from these large river basins provide a useful tool to calculate the average upper crustal composition because they are large-scale integrated samples of the weathering products of the present-day Upper Continental Crust (UCC). Two different and complementary calculations were done to estimate the average lead isotopic composition of the UCC. The first, based on the flux weighted average of particulate lead delivered by the rivers, gave values of 19.07, 15.74 and 39.35 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. To avoid over-estimating the contribution of orogenic areas, which produces a bias (because the flux of particulate lead depends strongly on the physical erosion rate), a second calculation was done by averaging with drainage areas of each river basin. This gave values of 18.93, 15.71 and 39.03 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. These direct calculations of the lead isotopic composition of the UCC are similar and are in agreement with previous estimates made using an indirect approach.     

湘东南铜山岭铅锌多金属矿床成矿时代与成矿物质来源——Sm-Nd等时线年龄和Pb同位素证据

铜山岭铅锌多金属矿床位于扬子地块湘南-桂东北坳陷与华夏地块粤北坳陷的拼贴部位,是中国南岭多金属成矿区代表性矿床之一。为确定矿床成矿时代,挑选铜山岭铅锌多金属矿床中含矿矽卡岩的石榴子石进行Sm-Nd同位素定年,获得的等时线年龄为173±3Ma,指示成矿作用发生于燕山早期。对金属硫化物矿物进行了Pb同位素分析,其~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb、~(208)Pb/~(204)Pb平均值分别为18.602、15.701、38.729,表明成矿物质来源于相对富集铀铅、略微亏损钍铅的上地壳源区。从(~(207)Pb/~(204)Pb)i-(~(206)Pb/~(204)Pb)i铅同位素演化模式图可知,寄主花岗闪长岩是铜山岭铅锌多金属矿床的重要物质来源,且成矿物质中可能含有寄存在花岗闪长岩中的地幔组分。