Plesovice zircon : A new natural reference material for U-Pb and Hf isotopic microanalysis

We present the first finding of continental crust-derived Precambrian zircons in garnet/spinel pyroxenite veins within mantle xenoliths carried by the Neogene Hannuoba basalt in the central zone of the North China Craton (NCC). Petrological and geochemical features indicate that these mantle-derived composite xenoliths were formed by silicic melt^lherzolite interaction. The Precambrian zircon ages can be classified into three age groups of 2·4^2·5 Ga, 1·6^2·2 Ga and 0·6^1·2 Ga, coinciding with major geological events in the NCC. These Precambrian zircons fall in the field of continental granitoid rocks in plots of U/Yb vs Hf and Y. Their igneous-type REE patterns and metamorphic zircon type CL images indicate that they were not crystallized during melt^peridotite interaction and subsequent high-pressure metamorphism.The 2·5 Ga zircons have positive eHf(t) values (2·9^10·6), whereas the younger Precambrian zircons are dominated by negative eHf(t) values, indicating an ancient continental crustal origin.These observations suggest that the Precambrian zircons were xenocrysts that survived melting of recycled continental crustal rocks and were then injected with silicate melt into the host peridotite. In addition to the Precambrian zircons, igneous zircons of 315 3 Ma (2 ), 80^170 Ma and 48^64 Ma were separated from the garnet/spinel pyroxenite veins; these provide evidence for lower continental crust and oceanic crust recycling-induced multi-episodic melt^peridotite interactions in the central zone of the NCC. The combination of the positive eHf(t) values (2·91^24·6) of the 315 Ma zircons with the rare occurrence of 302^324 Ma subduction-related diorite^granite plutons in the northern margin of the NCC implies that the 315 Ma igneous zircons might record melt^peridotite interactions in the lithospheric mantle induced by Palaeo-Asian oceanic crust subduction. Igneous zircons of age 80^170 Ma generally coexist with the Precambrian metamorphic zircons and have lower Ce/Yb and Th/U ratios, higher U/Yb ratios and greater negative Eu anomalies.The eHf(t) values of these zircons vary greatly from ^47·6 to 24·6.The 170^110 Ma zircons are generally characterized by negative eHf(t) values, whereas the 110^100 Ma zircons have positive eHf(t) values.These observations suggest that melt^peridotite interactions at 80^170 Ma were induced by partial melting of recycled continental crust. The 48^64 Ma igneous zircons are characterized by negligible Ce anomalies, unusually high REE, U and Th contents, and positive eHf(t) values.These features imply that the melt^peridotite interactions at 48^64 Ma could be associated with a depleted mantle-derived carbonate melt or fluid.

Continental and Oceanic Crust Recycling-induced Melt^Peridotite Interactions in the Trans-North China Orogen: U^Pb Dating, Hf Isotopes and Trace Elements in Zircons from Mantle Xenoliths

One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas Such materials are of critical importance to many applications involving catalysis, separation and gas storage The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g(-1) (ref 2) Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g(-1) (ref 3) But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g(-1) (refs 4-7) Despite this, no method of determining the upper limit in surface area for a material has yet been found Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g(-1) This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules--attributes not previously combined in one material

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A route to high surface area, porosity and inclusion of large molecules in crystals

The Lu–Hf and Sm–Nd isotopic composition of CHUR: Constraints from unequilibrated chondrites and implications for the bulk composition of terrestrial planets

Major and trace element composition of the depleted MORB mantle (DMM)

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.

https://science.sciencemag.org/content/sci/293/5530/683.full.pdf

Calibration of the lutetium-hafnium clock.

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.

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

[1] The application of multiple collector inductively coupled plasma source mass spectrometry (MC-ICPMS) to 176Lu-176Hf and 92Nb-92Zr chronometry has been hampered by complex Zr-Hf purification procedures that involve multiple ion exchange column steps. This study presents a single-column separation procedure for purification of Hf and Lu by ion exchange using Eichrom® Ln-Spec resin. The sample is loaded in pure HCl, and element yields are not dependent on the sample matrix. For 92Nb-92Zr chronometry, a one-column procedure for purification of Zr using Biorad® AG-1-× 8 resin is described. Titanium and Mo are completely removed from the Zr, thus enabling accurate 92Zr measurements. Zirconium and Nb are quantitatively separated from rock samples using Eichrom Ln-Spec resin, allowing measurements of Zr/Nb with a precision of better than ±5% (2σ). The Ln-Spec and anion resin procedures may be combined into a three-column method for separation of Zr-Nb, Hf, Ta, and Lu from rock samples. For the first time, this procedure permits combined isotope dilution measurements of Nb/Ta, Zr/Hf, and Lu/Hf using a mixed 94Zr-176Lu-180Hf-180Ta tracer. Analytical protocols for Zr and Hf isotope measurements using the Micromass Isoprobe, a second generation, single-focusing MC-ICPMS, are reported. Using the Isoprobe at Munster, 2σ external precisions of ±0.5ɛ units for Hf and Zr isotope measurements are achieved using as little as 5 ng (Hf) to 10 ng (Zr) of the element. The 176Hf/177Hf and Lu/Hf for rock reference materials agree well with other published MC-ICPMS and thermal ionization mass spectrometry (TIMS) data.

Separation of high field strength elements (Nb, Ta, Zr, Hf) and Lu from rock samples for MC‐ICPMS measurements

It has been assumed that Nb and Ta are not fractionated during differentiation processes on terrestrial planets and that both elements are lithophile. High-precision measurements of Nb/Ta and Zr/Hf reveal that Nb is moderately siderophile at high pressures. Nb/Ta values in the bulk silicate Earth (14.0 ± 0.3) and the Moon (17.0 ± 0.8) are below the chondritic ratio of 19.9 ± 0.6, in contrast to Mars and asteroids. The lunar Nb/Ta constrains the mass fraction of impactor material in the Moon to less than 65%. Moreover, the Moon-forming impact can be linked in time with the final core-mantle equilibration on Earth 4.533 billion years ago.

https://science.sciencemag.org/content/sci/301/5629/84.full.pdf

Carsten Münker

Papers

Calibration of the lutetium-hafnium clock.

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

Separation of high field strength elements (Nb, Ta, Zr, Hf) and Lu from rock samples for MC‐ICPMS measurements

Evolution of planetary cores and the Earth-Moon system from Nb/Ta systematics.

Nb/Ta and Zr/Hf in ocean island basalts — Implications for crust–mantle differentiation and the fate of Niobium