Earth's geodynamic evolution constrained by 182W in Archean seawater.

Radiogenic isotope systems are important geochemical tools to unravel geodynamic processes on Earth. Applied to ancient marine chemical sediments such as banded iron formations, the short-lived 182Hf-182W isotope system can serve as key instrument to decipher Earth's geodynamic evolution. Here we show high-precision 182W isotope data of the 2.7 Ga old banded iron formation from the Temagami Greenstone Belt, NE Canada, that reveal distinct 182W differences in alternating Si-rich (7.9 ppm enrichment) and Fe-rich (5.3 ppm enrichment) bands reflecting variable flux of W from continental and hydrothermal mantle sources into ambient seawater, respectively. Greater 182W excesses in Si-rich layers relative to associated shales (5.9 ppm enrichment), representing regional upper continental crust composition, suggest that the Si-rich bands record the global rather than the local seawater 182W signature. The distinct intra-band differences highlight the potential of 182W isotope signatures in banded iron formations to simultaneously track the evolution of crust and upper mantle through deep time.

The Earth's missing lead may not be in the core.

Relative to the CI chondrite class of meteorites (widely thought to be the 'building blocks' of the terrestrial planets), the Earth is depleted in volatile elements. For most elements this depletion is thought to be a solar nebular signature, as chondrites show depletions qualitatively similar to that of the Earth. On the other hand, as lead is a volatile element, some Pb may also have been lost after accretion. The unique (206)Pb/(204)Pb and (207)Pb/(204)Pb ratios of the Earth's mantle suggest that some lead was lost about 50 to 130 Myr after Solar System formation. This has commonly been explained by lead lost via the segregation of a sulphide melt to the Earth's core, which assumes that lead has an affinity towards sulphide. Some models, however, have reconciled the Earth's lead deficit with volatilization. Whichever model is preferred, the broad coincidence of U-Pb model ages with the age of the Moon suggests that lead loss may be related to the Moon-forming impact. Here we report partitioning experiments in metal-sulphide-silicate systems. We show that lead is neither siderophile nor chalcophile enough to explain the high U/Pb ratio of the Earth's mantle as being a result of lead pumping to the core. The Earth may have accreted from initially volatile-depleted material, some lead may have been lost to degassing following the Moon-forming giant impact, or a hidden reservoir exists in the deep mantle with lead isotope compositions complementary to upper-mantle values; it is unlikely though that the missing lead resides in the core.

Rapid accretion and early core formation on asteroids and the terrestrial planets from Hf-W chronometry.

The timescales and mechanisms for the formation and chemical differentiation of the planets can be quantified using the radioactive decay of short-lived isotopes. Of these, the (182)Hf-to-(182)W decay is ideally suited for dating core formation in planetary bodies. In an earlier study, the W isotope composition of the Earth's mantle was used to infer that core formation was late (> or = 60 million years after the beginning of the Solar System) and that accretion was a protracted process. The correct interpretation of Hf-W data depends, however, on accurate knowledge of the initial abundance of (182)Hf in the Solar System and the W isotope composition of chondritic meteorites. Here we report Hf-W data for carbonaceous and H chondrite meteorites that lead to timescales of accretion and core formation significantly different from those calculated previously. The revised ages for Vesta, Mars and Earth indicate rapid accretion, and show that the timescale for core formation decreases with decreasing size of the planet. We conclude that core formation in the terrestrial planets and the formation of the Moon must have occurred during the first approximately 30 million years of the life of the Solar System.

Calibration of the lutetium-hafnium clock.

Well-defined constants of radioactive decay are the cornerstone of geochronology and the use of radiogenic isotopes to constrain the time scales and mechanisms of planetary differentiation. Four new determinations of the lutetium-176 decay constant (lambda176Lu) made by calibration against the uranium-lead decay schemes yield a mean value of 1.865 +/- 0.015 x 10(-11) year(-1), in agreement with the two most recent decay-counting experiments. Lutetium-hafnium ages that are based on the previously used lambda176Lu of 1.93 x 10(-11) to 1.94 x 10(-11) year(-1) are thus approximately 4% too young, and the initial hafnium isotope compositions of some of Earth's oldest minerals and rocks become less radiogenic relative to bulk undifferentiated Earth when calculated using the new decay constant. The existence of strongly unradiogenic hafnium in Early Archean and Hadean zircons implies that enriched crustal reservoirs existed on Earth by 4.3 billion years ago and persisted for 200 million years or more. Hence, current models of early terrestrial differentiation need revision.

92Nb-(92)Zr and the Early Differentiation History of Planetary Bodies.

The niobium-92-zirconium-92 ((92)Nb-(92)Zr) extinct radioactive decay system (half-life of about 36 million years) can place new time constraints on early differentiation processes in the silicate portion of planets and meteorites. Zirconium isotope data show that Earth and the oldest lunar crust have the same relative abundances of (92)Zr as chondrites. (92)Zr deficits in calcium-aluminum-rich inclusions from the Allende meteorite constrain the minimum value for the initial (92)Nb/(93)Nb ratio of the solar system to 0.001. The absence of (92)Zr anomalies in terrestrial and lunar samples indicates that large silicate reservoirs on Earth and the moon (such as a magma ocean residue, a depleted mantle, or a crust) formed more than 50 million years after the oldest meteorites formed.

Pb-Nd Isotopes Indicate the Origin of Island Arc Terranes in the Early Paleozoic Pacific.

The Takaka Terrane in New Zealand is one of the best exposed arc fragments of the early Paleozoic Australian-Antarctic convergent margin and constitutes one of the most outboard terranes of this margin in paleogeographic reconstructions. Pb-Nd isotope compositions of clinopyroxenes from the Cambrian Devil River Volcanics of the Takaka Terrane enable identification of the location of the terrane in the Paleo-Pacific Ocean. The Devil River Volcanics, a suite of primitive arc and back-arc rocks, are interbedded with the partly continent-derived Haupiri Group sediments. Extremely radiogenic Pb and unradiogenic Nd compositions in the arc rocks cannot be explained by assimilation of the Haupiri Group sediments or a continental basement of such a composition. Pb isotope compositions of the Takaka Terrane sediments are much less radiogenic and overlap with crustal compositions of the Lachlan Fold Belt in Australia, suggesting that both units are derived from one source, the Australian-Antarctic Pacific margin. Pb-Nd isotope compositions in the Devil River Volcanics reflect contamination of their mantle sources by subducted sediments derived from Archean provinces in either Antarctica or Laurentia. Both provinces show characteristically high 207Pb/204Pb500 and were located at the Pacific rim in the Cambrian. Mixing between mantle and Proterozoic continental material from present western South America or eastern Laurentia cannot explain the high 207Pb/204Pb500 in the New Zealand rocks. As in New Zealand, extreme spreads in Pb-Nd isotope compositions in other Cambrian volcano-sedimentary sequences in southeast Australia and Tasmania can be explained by the same model, suggesting that all these fragments originated along the Australian-Antarctic Gondwana margin. Pb isotope compositions of arc rocks, therefore, provide a new tool for terrane analysis in the early Paleozoic Pacific ocean.

Determination of niobium(V) and tantalum(V) as 4-(2-pyridylazo)resorcinol-citrate ternary complexes in geological materials by ion-interaction reversed-phase high-performance liquid chromatography.

A method for the simultaneous separation and determination of Nb(V) and Ta(V) as ternary complexes formed with 4-(2-pyridylazo)resorcinol (PAR) and citrate was developed using ion-interaction reversed-phase high-performance liquid chromatography on a C18 column. Method parameters, such as pre-column complex formation conditions and composition of the complexes were investigated using spectrophotometry and HPLC. Under the optimum conditions, the Nb(V) and Ta(V) complexes were eluted within 12 min with a mobile phase of methanol-water (32:68, v/v) containing 5 mM acetate, 5 mM TBABr and 5 mM citrate buffer at pH 6.5, with detection at 540 nm. A typical separation efficiency was 33,000 and 20,000 theoretical plates per metre for Nb(V) and Ta(V), respectively. The relative standard deviation of retention times for the Nb(V) and Ta(V) complexes were 0.16% and 0.17% and for peak areas were 0.28% and 1.36%, respectively. The detection limits (signal-to-noise ratio = 3) for Nb(V) and Ta(V) were 0.4 ppb and 1.4 ppb, respectively. Results obtained for standard reference rock samples agreed well with certified values and results obtained by inductively coupled plasma MS.