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.     

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).     

Miocene dislocations during the formation of the Sea of Japan basin: Case study of Tsushima Island

Lower Miocene rocks of the Taishu Group accumulated in the Tsushima pull-apart graben, which downwarped and was filled with sediments at a particularly high rate (about 2700 m/Ma), in the background of northeastern regional shortening. A considerable part of the sedimentary prism is composed of material supplied by landslide blocks from the shallow shelf. Folding and penetration of granite intrusions on Tsushima Island occurred ca. 15 Ma ago, simultaneously with the main phase of opening of the Sea of Japan, in the field of different, northwestern shortening, which had a local character and was related to clockwise rotation of the Southwestern Japan block. These rotations in turn could have been the result of an intensive rifting episode in the Central and Honshu basins of the Sea of Japan, which are located north of Tsushima Island.     

http://www.sciencedirect.com/science/article/pii/S1674987112001272

Our blue planet Earth has long been regarded to carry full of nutrients for hosting life since the birth of the planet.Here we speculate the processes that led to the birth of early life on Earth and its aftermath, finally leading to the evolution of metazoans.We evaluate:（1） the source of nutrients,（2） the chemistry of primordial ocean,（3） the initial mass of ocean,and（4） the size of planet.Among the life-building nutrients,phosphorus and potassium play a key role.Only three types of rocks can serve as an adequate source of nutrients:（a） continent-forming TTG（granite）,enabling the evolution of primitive life to metazoans;（b） primordial continents carrying anorthosite with KREEP（Potassium,Rare Earth Elements, and Phosphorus） basalts,which is a key to bear life;（c） carbonatite magma,enriched in radiogenic elements such as U and Th,which can cause mutation to speed up evolution and promote the birth of new species in continental rift settings.The second important factor is ocean chemistry.The primordial ocean was extremely acidic（pH = 1-2） and enriched in halogens（CI,F and others）,S,N and metallic elements（Cd,Cu,Zn,and others）,inhibiting the birth of life.Plate tectonics cleaned up these elements which interfered with RNA.Blue ocean finally appeared in the Phanerozoic with pH = 7 through extensive interaction with surface continental crust by weathering,erosion and transportation into ocean.The initial ocean mass was also important.The birth of life and aftermath of evolution was possible in the habitable zone with 3-5 km deep ocean which was able to supply sufficient nutrients. Without a huge landmass,nutrients cannot be supplied into the ocean only by ridge-hydrothermal circulation in the Hadean.Finally,the size of the planet plays a crucial role.Cooling of massive planets is less efficient than smaller ones,so that return-flow of seawater into mantle does not occur until central stars finish their main sequence.Due to the suitable size of Earth,the dawn of Phanerozoic witnessed the initiation of return-flow of seawater into the mantle,leading to the emergence of huge landmass above sea-level,and the distribution of nutrients on a global scale.Oxygen pump also played a critical role to keep high-PO₂ in atmosphere since then,leading to the emergence of ozone layer and enabling animals and plants to invade the land. To satisfy the tight conditions to make the Earth habitable,the formation mechanism of primordial Earth is an important factor.At first,a ’dry Earth’ must be made through giant impact,followed by magma ocean to float nutrient-enriched primordial continents（anorthosite + KREEP）.Late bombardment from asteroid belt supplied water to make 3-5 km thick ocean,and not from icy meteorites from Kuiper belt beyond cool Jupiter.It was essential to meet the above conditions that enabled the Earth as a habitable planet with evolved life forms.The tight constraints that we evaluate for birth and evolution of life on Earth would provide important guidelines for planetary scientists hunting for life in the exosolar planets.     

Investigating the Influence of Non‐Spectral Matrix Effects in the Determination of Twenty‐Two Trace Elements in Rock Samples by ICP‐QMS

The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, ¹¹³In and ²⁰³Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.