From measurements of Hf-Yb mixtures, we have found that the correction of isobaric interferences involving accepted Yb isotope ratios and reasonable estimates of mass bias result in a significantly under-corrected 176 Hf, which is proportional to the amount of Yb added. This can be explained by (1) a significant difference in the instrumental mass bias between Hf and Yb, and (2) that the accepted values for isotopic ratios within the Yb and/or Hf systems are incorrect. We have evaluated these possibilities by measuring mixed solutions of Yb and Hf on two MC-ICP-MS instruments and undertaking a series of REE fractionation experiments using a thermal ionisation mass spectrometer (TIMS). Our results indicate that the presently accepted abundances of the Yb isotopes are not appropriate. We present new values for Yb isotopic abundances based on the TIMS and MC-ICP-MS results. Using the newly defined Yb values, we demonstrate that Yb and Hf have similar levels of mass bias in plasma ionisation instruments, and that Hf isotope ratios can be used to correct Yb mass bias before subsequent correction of isobaric interference. A laser ablation comparison of Yb and Hf indicates that similar relationships exist, and can be applied to micro-analytical techniques where chemical separation is not possible.

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Hafnium 176 Hf/ 177 Hf isotope ratio variations in marine records are thought to reflect changes in continental weathering through time, but the behavior of Hf in rivers, and during weathering, is not well understood. Here, we present 176 Hf/ 177 Hf data for rivers, bedrock, soils, and leaching experiments for the Moselle basin, Vosges, France. These data strongly suggest that the 176 Hf/ 177 Hf composition of river waters is controlled by preferential dissolution of accessory phases (i.e., apatite, sphene) versus more resistant minerals (e.g., K-feldspar) and linked to the intensity of silicate weathering. Estimates for the global isotopic composition of riverine Hf suggest that the ocean Hf budget may be dominated by river input, and variations seen in marine records can be directly related to changes in silicate weathering intensity.

Temporal variations in Fe isotope compositions at three locations in the Pacific Ocean over the last 10 Ma are inferred from high-resolution analyses of three hydrogenetic ferromanganese crusts. Iron pathways to the central deep Pacific Ocean appear to have remained constant over the past 10 Ma, reflected by a remarkably constant Fe isotope composition, despite large changes in the Fe delivery rates to the surface ocean via dust. These results suggest that the Fe cycle in the deep ocean is decoupled from that in surface waters. By contrast, one ferromanganese crust from the Izu-Bonin (IB) back-arc/marginal basin of the W. Pacific exhibits large δ 56 Fe variations. In that crust, decreases in δ 56 Fe values correlate with increases in Mn, Mg, Ni, Cu, Zn, Mo, and V contents, and consistent with periods of intense hydrothermal input and increased growth rates. A second crust located within 100 km of the first IB sample does not record any of these periods of enhanced hydrothermal input. This probably reflects the isolated pathways