ALBERT

Description: It is well established that Hf weathers incongruently such that the isotopic compositions in seawater are offset from those of Nd relative to the correlation defined by bulk lithologies of the continental crust. Here we study this process in detail with new records of the seasonal variability of isotope compositions and concentrations of Hf and Nd in four Swiss rivers. The water has been filtered at a pore size of 0.45 mu m and therefore represents the truly dissolved and the colloidal pool of both elements. The studied rivers drain metamorphic (gneissic) or sedimentary (mixed carbonate/siliciclastic) lithologies. The dissolved isotope data are compared to the isotope compositions and concentrations of the suspended load and different fractions of the actual source rocks in the respective catchments, as well as to concomitant changes in the aqueous chemistry of the major elements. Dissolved Nd concentrations span similar ranges for all rivers, whereas Hf concentrations are one order of magnitude lower in the rivers that drain gneissic catchments compared to those draining sedimentary rocks. This primarily results from the retention of most of the Hf in the gneissic zircons, as indicated by the Hf budget of the gneisses, whereas Hf in the sedimentary catchments is readily weathered from fine detrital silicates. Large differences are found between the dissolved Hf isotope compositions of the rivers and those of the suspended load and the source rocks, consistent with the release of Hf from a radiogenic rock fraction during weathering. In the metamorphic catchments this primarily reflects that fact that zircons are barely accessible for weathering. The zircon-free portion of the rocks appears to weather congruently as the riverine Hf isotope compositions are similar to the zircon-free portion of the gneisses, rather than being distinctly more radiogenic. Leaching experiments performed to understand the riverine Hf budget in the sedimentary catchments reveal that the carbonate fraction of the sedimentary rocks is extremely radiogenic, yielding Hf isotope compositions up to epsilon(Hf) of + 208. However, the Hf concentrations in the carbonate fractions are too low to dominate the riverine Hf budget, which is instead controlled by the weathering of detrital silicate minerals. Two of the catchments, a metamorphic and a sedimentary one, show relatively systematic changes towards more radiogenic dissolved Hf isotope compositions as discharge increases. This suggests that continental runoff conditions could be a relevant parameter for the control of the seawater Hf isotope composition, whereby more congruent weathering is achieved during low discharge when Hf is increasingly derived from weathering-resistant unradiogenic minerals

Description: We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.