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.     

Mobile Pb-isotopes in Proterozoic sedimentary basins as guides for exploration of uranium deposits

Lead isotope ratios and associated trace element concentrations (U, Th and Pb) extracted by partial-leaching with 2% nitric acid from Proterozoic sandstones and basement rocks reveal much about the fluid evolution of sedimentary basins hosting unconformity-type uranium deposits. In addition, these techniques have great potential as a guide for exploration of uranium and other types of deposits in basins of any age. Isotope ratios of Pb in Proterozoic sandstones from basins known to contain high-grade uranium deposits are radiogenic at key geological localities and settings distal to known mineralization and particularly in altered zones proximal to mineralization. Sandstones completely cemented by quartz overgrowths typically have non-radiogenic Pb isotope ratios, indicating early closure of porosity and isolation of these rocks from later fluid events. Alternatively, the unconformity served as both a source of uranium and radiogenic Pb as well as an avenue for late-stage (<250–900 Ma) fluid flow. The mafic volcanic units, which are relatively reducing lithologies and therefore have removed uranium from basinal brines, have uranium-supported radiogenic Pb isotope ratios. Comparison of ²³⁸U/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb ratios is useful in determining the timing and nature of U and Pb migration before, during and after mineralization in these basins. This comparison can be used to delineate the presence of radiogenic Pb isotope ratios that are not internally supported by uranium and thorium in rocks, eventually providing the explorationist with geochemical vectors that point toward sites of high potential for economic uranium mineralization.     

Penglai Zircon Megacrysts: A Potential New Working Reference Material for Microbeam Determination of Hf–O Isotopes and U–Pb Age

We introduce a potential new working reference material – natural zircon megacrysts from an Early Pliocene alkaline basalt (from Penglai, northern Hainan Island, southern China) – for the microbeam determination of O and Hf isotopes, and U–Pb age dating. The Penglai zircon megacrysts were found to be fairly homogeneous in Hf and O isotopes based on large numbers of measurements by LA-multiple collector (MC)-ICP-MS and SIMS, respectively. Precise determinations of O isotopes by isotope ratio mass spectrometry (IRMS) and Hf isotopes by solution MC-ICP-MS were in good agreement with the statistical mean of microbeam measurements. The mean δ¹⁸O value of 5.31 ± 0.10‰ (2s) by IRMS and the mean ¹⁷⁶Hf/¹⁷⁷Hf value of 0.282906 ± 0.0000010 (2s) by solution MC-ICP-MS are the best reference values for the Penglai zircons. SIMS and isotope dilution-TIMS measurements yielded consistent ²⁰⁶Pb/²³⁸U ages within analytical uncertainties, and the preferred ²⁰⁶Pb/²³⁸U age was found to be 4.4 ± 0.1 Ma (95% confidence interval). The young age and variably high common Pb content make the Penglai zircons unsuitable as a primary U–Pb age reference material for calibration of unknown samples by microbeam analysis; however, they can be used as a secondary working reference material for quality control of U–Pb age determination for young (particularly < 10 Ma) zircon samples.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Lead contamination in a wetland watershed: isotopes as fingerprints of pollution

The Pb-isotope composition of soils and sediments has been measured from both highly contaminated and non-contaminated regions of Bayou Trepagnier, a bayou in southern Louisiana that has had oil refinery effluent discharged into it over the past 66 years. Spoil banks created by the dredging of the bayou bottom approximately 50 years ago are the main source of contamination within the ecosystem. The ²⁰⁶Pb/²⁰⁷Pb isotope composition of the contaminant is relatively constant averaging 1.275 ±0.008. A literature search reveals that such radiogenic values are typical of ores from southeastern Missouri. When surficial soil ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb isotope ratios are plotted against each other, a straight line is defined (r²=0.99). The linear correlation suggests mixing between Pb from the spoil banks and Pb from a natural source. The latter source may consist of Pb in soil that has been leached of its natural radiogenic component during weathering processes. Mixing calculations indicate that transport of contaminant Pb is widespread and occurs several hundred meters from the spoil banks. Despite the low Pb concentrations of some of the soils, the isotope data demonstrate that a significant amount of the Pb is derived from the pollutant source. Received: 12 July 1999 · Accepted: 14 September 1999     

Lead isotope constraints on the genesis of Pb–Zn deposits in the Neoproterozoic Vazante Group, Minas Gerais, Brazil

The Neoproterozoic Vazante Group at the western border of the São Francisco Craton, Brazil, hosts the largest Zn–Pb district in South America. Several authors have classified this mineral district as Mississippi Valley-type (MVT), based on the intimate association with carbonates and the epigenetic character of most ore bodies. In this paper, we present 47 new lead isotope data from four deposits located along the 300 km N–S Vazante–Paracatu–Unai linear trend. Pb isotope ratios indicate sources with relatively high U/Pb and Th/Pb ratios. Considering the ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios as indicative parameters for the source, we suggest an upper crustal source for the metals. The small variation on the Pb isotope ratios compared to those observed in the classical MVT deposits, and other geological, fluid inclusion and sulphur isotopic data indicates a metallogenic event of long duration. It was characterized by focused circulation of hydrothermal fluids carrying metals from the basement rocks and from the sedimentary pile. The data obtained are more compatible with an evolution model similar to that of IRISH-type deposits. The existence of three Pb isotopic populations could be the result of regional differences in composition of the source rocks and in the fluid–rock interaction since the mineralization is a long-term process.     

Anomalous lead isotope ratios and provenance of offshore sediments,Gulf of Carpentaria,northern Australia

Anomalous Pb isotope ratios measured by Inductively Coupled Plasma Mass Spectrometry in terrigenous marine sediments (<63 μm fraction) from the Gulf of Carpentaria originated from depositional mixing of clay/silt with average modern crustal Pb isotope ratios and detrital monazite with high ²⁰⁸Pb/²⁰⁶Pb and low ²⁰⁷Pb/²⁰⁶Pb. This interpretation is supported by strong correlations between Pb isotope ratio and Th, U and light rare‐earth element concentrations in the sediments as well as by monazite compositional data. A likely source of the detrital monazite is the western portion of the Georgetown Inlier of mainly Proterozoic S‐type granitic rocks. A clear distinction between Pb isotope ratios in sediments deposited from the Norman and Bynoe Rivers in the southeast Gulf of Carpentaria and the persistence of catchment‐specific Pb isotope ratios 45 km offshore suggest that Pb isotope data are useful in tracing the provenance of terrigenous offshore sediments when the source rocks of catchments show sufficient chemical and/or mineralogical variation.     

Albany K-Feldspar: A New Pb Isotope Reference Material

Lead isotopes are a powerful and versatile tool to elucidate fundamental geological problems related to the formation and evolution of continental crust. K-feldspar is a popular target for Pb isotope measurement as it is prevalent in many rock types and tends to capture the initial Pb isotope composition of its parental magma. We present data for a new Pb isotope reference material: Albany K-feldspar; as well as updated data for Shap K-feldspar. Results of Pb double-spike TIMS for Albany K-feldspar are ²⁰⁶Pb/²⁰⁴Pb = 16.7872 ± 0.0062, ²⁰⁷Pb/²⁰⁴Pb = 15.5640 ± 0.0056, and ²⁰⁸Pb/²⁰⁴Pb = 36.6600 ± 0.0168 (2s). TIMS measurement results for Shap K-feldspar indicate two isotopically distinct Pb populations. LA-MC-ICP-MS, with a spatial resolution as high as 15 μm, indicates a homogeneous Pb isotopic composition in Albany K-feldspar. In accord with previous studies, our results show that scatter in the measured Pb isotope ratios, related to the low natural isotopic abundance of ²⁰⁴Pb, along with the effect of isobaric ²⁰⁴Hg-²⁰⁴Pb interference, increases at lower count rates. However, the mean Pb isotope ratios measured via LA-MC-ICP-MS using a range of spot sizes are in excellent agreement with TIMS results thus highlighting the feasibility of Pb isotope determination via LA-MC-ICP-MS to access geological information preserved in small crystals, including mineral inclusions.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).     

Pb concentrations and isotope ratios of soil O and C horizons in Nord-Trøndelag,central Norway: Anthropogenic or natural sources?

Soil O and C horizon samples (N = 752) were collected at a sample density of 1 site/36 km² in Nord-Trøndelag and parts of Sør-Trøndelag (c. 25,000 km²), and analysed for Pb and three of the four naturally occurring Pb isotopes (²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb) in a HNO₃/HCl extraction. Soil O and C horizons are decoupled in terms of both Pb concentrations and Pb isotope ratios. In the soil C horizon the Grong-Olden Culmination, a continuous exposure of the Precambrian crystalline basement across the general grain of the Caledonian orogen, is marked by a distinct ²⁰⁶Pb/²⁰⁷Pb isotope ratio anomaly. No clear regional or even local patterns are detected when mapping the Pb isotope ratios in the soil O horizon samples. Variation in the isotope ratios declines significantly from the soil C to the O horizon. On average, Pb concentrations in the O horizon are four times higher and the ²⁰⁶Pb/²⁰⁷Pb isotope ratio is shifted towards a median of 1.15 in comparison to 1.27 in the C horizon. It is demonstrated that natural processes like weathering in combination with plant uptake need to be taken into account in order to distinguish anthropogenic input from natural influences on Pb concentration and the ²⁰⁶Pb/²⁰⁷Pb isotope ratio in the soil O horizon.     

Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

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.     

Lead Isotopic Composition in Biogenic Certified Reference Materials Determined by Different ICP‐based Mass Spectrometric Techniques

This work presents data for the radiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) in nine biogenic certified reference materials (NIST SRM 1515, 1566b, 1570a, 1573a, 1575a; BCR 100, BCR 101, BCR 670 and IAEA 359), which are suitable for analytical quality control in environmental research. The results were obtained using three different types of ICP‐based mass spectrometer (quadrupole‐based/magnetic sector field single‐collector ICP‐MS instruments and a multi‐collector ICP‐MS) and applying different mass bias correction procedures (calibrator‐sample bracketing and external Tl normalisation) with and without Pb separation from the matrix using ion exchange chromatography. In the majority of the samples, the measurements from all three of the ICP‐MS instruments were in agreement within ± 0.1%, despite the lower analytical precision of the single‐collector ICP‐MS instruments. We demonstrate that the presence of the sample matrix did not significantly influence the Pb isotopic ratios measured by magnetic sector field ICP‐MS, whereas the use of the two different mass bias corrections resulted in a systematic difference of 0.09% for the ²⁰⁸Pb/²⁰⁶Pb ratio.     

U-Pb Age Determination for Seven Standard Zircons using Inductively Coupled Plasma–Mass Spectrometry Coupled with Frequency Quintupled Nd-YAG (λ = 213 nm) Laser Ablation System: Comparison with LA-ICP-MS Zircon Analyses with a NIST Glass Reference Material

This paper evaluates the analytical precision, accuracy and long‐term reliability of the U‐Pb age data obtained using inductively coupled plasma–mass spectrometry (ICP‐MS) with a frequency quintupled Nd‐YAG (λ = 213nm) laser ablation system. The U‐Pb age data for seven standard zircons of various ages, from 28 Ma to 2400 Ma (FCT, SL13, 91500, AS3, FC1, QGNG and PMA7) were obtained with an ablation pit size of 30 μm diameter. For ²⁰⁷Pb/²⁰⁶Pb ratio measurement, the mean isotopic ratio obtained on National Institute of Standards and Technology (NIST) SRM610 over 4 months was 0.9105 ± 0.0014 (n = 280, 95% confidence), which agrees well with the published value of 0.9096. The time‐profile of Pb/U ratios during single spot ablation showed no significant difference in shape from NIST SRM610 and 91500 zircon standards. These results encouraged the use of the glass standard as a calibration standard for the Pb/U ratio determination for zircons with shorter wavelength (λ = 213 nm) laser ablation. But ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages obtained by this method for seven zircon standards are systematically younger than the published U‐Pb ages obtained by both isotope dilution–thermal ionization mass spectrometry (ID‐TIMS) and sensitive high‐resolution ion‐microprobe (SHRIMP). Greater discrepancies (3–4% younger ages) were found for the ²⁰⁶Pb/²³⁸U ages for SL13, AS3 and 91500 zircons. The origin of the differences could be heterogeneity in Pb/U ratio on SRM610 between the different disks, but a matrix effect accuracy either in the ICP ion source or in the ablation‐transport processes of the sample aerosols cannot be neglected. When the ²⁰⁶Pb/²³⁸U (= 0.2302) newly defined in the present study is used, the measured ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages for the seven zircon standards are in good agreement with those from ID‐TIMS and SHRIMP within ±2%. This suggests that SRM610 glass standard is suitable for ICP‐MS with laser ablation sampling (LA‐ICP‐MS) zircon analysis, but it is necessary to determine the correction factor for ²⁰⁶Pb/²³⁸U by measuring several zircon standards in individual laboratories.     

Assessment of Nanosecond Laser Ablation Multi‐Collector Inductively Coupled Plasma‐Mass Spectrometry for Pb and Sr Isotopic Determination in Archaeological Glass: Mass Bias Correction Strategies and Results for Corning Glass Reference Materials

This work presents an evaluation of various methods for in situ high‐precision Sr and Pb isotopic determination in archaeological glass (containing 100–500 μg g^?1 target element) by nanosecond laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (ns‐LA‐MC‐ICP‐MS). A set of four soda‐lime silicate glasses, Corning A–D, mimicking the composition of archaeological glass and produced by the Corning Museum of Glass (Corning, New York, USA), were investigated as candidates for matrix‐matched reference materials for use in the analysis of archaeological glass. Common geological reference materials with known isotopic compositions (USGS basalt glasses BHVO‐2G, GSE‐1G and NKT‐1G, soda‐lime silicate glass NIST SRM 610 and several archaeological glass samples with known Sr isotopic composition) were used to evaluate the ns‐LA‐MC‐ICP‐MS analytical procedures. When available, ns‐LA‐MC‐ICP‐MS results for the Corning glasses are reported. These were found to be in good agreement with results obtained via pneumatic nebulisation (pn) MC‐ICP‐MS after digestion of the glass matrix and target element isolation. The presence of potential spectral interference from doubly charged rare earth element (REE) ions affecting Sr isotopic determination was investigated by admixing Er and Yb aerosols by means of pneumatic nebulisation into the gas flow from the laser ablation system. It was shown that doubly charged REE ions affect the Sr isotope ratios, but that this could be circumvented by operating the instrument at higher mass resolution. Multiple strategies to correct for instrumental mass discrimination in ns‐LA‐MC‐ICP‐MS and the effects of relevant interferences were evaluated. Application of common glass reference materials with basaltic matrices for correction of ns‐LA‐MC‐ICP‐MS isotope data of archaeological glasses results in inaccurate Pb isotope ratios, rendering application of matrix‐matched reference materials indispensable. Correction for instrumental mass discrimination using the exponential law, with the application of Tl as an internal isotopic standard element introduced by pneumatic nebulisation and Corning D as bracketing isotopic calibrator, provided the most accurate results for Pb isotope ratio measurements in archaeological glass. Mass bias correction relying on the power law, combined with intra‐element internal correction, assuming a constant ⁸⁸Sr/⁸⁶Sr ratio, yielded the most accurate results for ⁸⁷Sr/⁸⁶Sr determination in archaeological glasses     

The Diamantina Monazite: A New Low‐Th Reference Material for Microanalysis

Most monazite reference materials (RMs) for in situ U‐Pb geochronology are rich in Th; however, many hydrothermal ore deposits contain monazite that is low in trace element contents, including Th, U and Pb. Because of potential problems with matrix effects and the lack of appropriate matrix‐matched RMs, such variations can bias dating of hydrothermal deposits. In this paper, we describe a polycrystalline low‐U and low‐Th Diamantina monazite from the Espinhaço Range, SE Brazil. It has a U‐Pb ID‐TIMS weighted mean ²⁰⁷Pb^*/²³⁵U ratio of 0.62913 ± 0.00079, ²⁰⁶Pb^*/²³⁸U of 0.079861 ± 0.000088 and ²⁰⁷Pb^*/²⁰⁶Pb^* of 0.057130 ± 0.000031, yielding a weighted mean ²⁰⁶Pb^*/²³⁸U date of 495.26 ± 0.54 Ma (95% c.l.). In situ dates acquired with different methods (LA‐(Q, SF, MC)‐ICP‐MS and SIMS) are within uncertainty of the ID‐TIMS data. U‐Pb LA‐(Q, MC)‐ICP‐MS runs, using Diamantina as a primary RM, reproduced the ages of other established RMs within < 1% deviation. The LA‐MC‐ICP‐MS analyses yielded homogeneous Sm‐Nd isotopic compositions (¹⁴³Nd/¹⁴⁴Nd = 0.511427 ± 23, 2s; ¹⁴⁷Sm/¹⁴⁴Nd = 0.1177 ± 13, 2s) and εNd_(495 Ma) of ?18.7 ± 0.5 (2s). SIMS oxygen isotope determinations showed measurement reproducibility better than ± 0.3‰ (2s), confirming Diamantina's relative homogeneity at test portion masses below 1 ng.     

Pb isotope signatures of sediments from Guanabara Bay, SE Brazil: Evidence for multiple anthropogenic sources

Sediments from Guanabara Bay and two rivers were analyzed for Pb isotope composition. The results define linear groups interpreted as different sources of Pb. The samples from Iriri and Surui rivers present different Pb compositions probably resulting from two active pollutants which are transported in the waters to the Guanabara Bay, where they are mixed. The ²⁰⁶Pb/²⁰⁷Pb values of 1.151 and 1.091 presented here are in the range of Brazilian galena ore signature.     

U–Th–Pb–REE systematics of organic-rich shales from the ca. 2.15 Ga Sengoma Argillite Formation, Botswana: Evidence for oxidative continental weathering during the Great Oxidation Event

The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere during deposition. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading even for drill core samples. Because both of these elements radioactively decay and produce lead isotopes, the Pb isotope composition may reflect the depositional Th/U ratio, although the Th/U ratios induced by changes shortly after deposition may not be distinguished from the true depositional Th/U ratios. In order to effectively evaluate the time-integrated Th/U ratio (κ_a), values for the initial depositional Pb isotope composition must be determined or accepted from the models for the whole Earth.While the timing for the rise of atmospheric oxygen is reasonably well constrained now, its effect on continental weathering and ocean redox state remains poorly constrained and debated. The ca. 2.15 Ga Sengoma Argillite Formation of Botswana contains organic-rich shales deposited during the Great Oxidation Event. The slope of the ²⁰⁷Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb array of shales from the Sengoma Argillite Formation corresponds to a Pb–Pb age that is within analytical error of the depositional age and is, therefore, inferred to be the time by which the time-integrated thorogenic and uranogenic lead growth started. The time-integrated lead growth corresponds to an average κ_a of 2.63 (± 0.62, 1σ) for the organic-rich shales of the Sengoma Argillite Formation. This is lower than Th/U ratios measured in Archean shale suites or estimated for the Archean–Proterozoic average upper continental crust [Taylor, S.R. and McLennan, S.M., 1985. The Continental Crust: Its Composition and Evolution. Blackwell, Oxford, 312 pp.], which indicates that these samples were enriched in uranium with respect to thorium (and perhaps lead) at the time of deposition. In the modern ocean, sediments are enriched in uranium under reducing conditions by reduction of the water-soluble uranyl ion, which is delivered to the ocean by oxidative weathering of continental crust. To evaluate the potential mobility of Th, U, and Pb during post-depositional processes, the concentrations of the rare earth elements (REE) were also determined. Interelement ratios of the largely immobile REE (in this study, La/Nd and Gd/Er) can be used as a proxy for the Th/U ratio, as the geochemical behavior of the lanthanide and actinide elements is similar under a variety of conditions. Furthermore, close similarity in the chondrite-normalized REE patterns and small range in La/Nd and Gd/Er ratios in studied samples indicate that variations in κ_a values are not likely to have been controlled by mixing of one or more REE-, Th-, and U-rich heavy minerals from the multiple detrital sources. Our study of shales from the ca. 2.15 Ga Sengoma Argillite Formation indicates that decoupling of U from Th, most likely related to the oxidative continental weathering, began by 2.15 Ga, at the latest.     

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.     

The thermal history of the Acapulco meteorite and its parent body deduced from U/Pb systematics in mineral separates and bulk rock fragments

U/Pb systematics of the Acapulco meteorite have been determined on phosphate and feldspar separates and on grain size fractions of bulk material. The latter show an enrichment of U and Th with respect to CI chondrites and a low (∼1) Th/U ratio. This is consistent with the model that the majority of U and Th was added early by a low temperature melt to the Acapulco precursor. The feldspar exhibits a Pb isotope composition that is close to the primordial Pb composition. Mineral separates and bulk fractions define a ²⁰⁷Pb/²⁰⁶Pb isochron. The age corresponds to 4555.9 ± 0.6 Ma. This age anchors the thermal evolution of the Acapulco parent body into an absolute time scale. Evaluation of the Hf/W and U/Pb records with the cooling rates deduced from mineralogical investigations confirms the idea that the Acapulco parent body was fragmented during its cooling. The U/Pb system precisely dates this break-up at 4556 ± 1 Ma.