ALBERT

Description: We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from −0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (−0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (−0.39 to −0.07‰) with a mean of −0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (−0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo concentrations of all the ultramafic xenoliths of 40–400 ppb, similar to or, significantly higher than, current estimates for the BSE (39 ppb). On this basis a revised best estimate of the Mo content in the BSE based on these concentrations would be in the range 113–180 ppb, significantly higher than previously assumed. These values are similar to the levels of depletion in the other refractory moderately siderophile elements W, Ni and Co. A simpler explanation may be that the subcontinental lithospheric mantle has been selectively enriched in Mo leading to the higher concentrations observed. Cryptic melt metasomatism would be difficult to reconcile with the high Mo/Ce of the most LREE depleted xenoliths. Ancient Mo-enriched subducted components would be expected to have heavy δ98/95Mo, which is not observed. The Mo isotope composition of the BSE, cannot be reliably resolved from that of chondrites at this time despite experimental evidence for metal–silicate fractionation. An identical isotopic composition might result from core–mantle differentiation under very high temperatures such as were associated with the Moon-forming Giant Impact, or from the BSE inventory reflecting addition of moderately siderophile elements from an oxidised Moon-forming impactor (O'Neill, 1991). However, the latter would be inconsistent with the non-chondritic radiogenic W isotopic composition of the BSE. Based on mantle fertility arguments, Mo in the BSE could even be lighter (lower 98/95Mo) than that in chondrites, which might be explained by loss of S rich liquids from the BSE during core formation (Wade et al., 2012). Such a late removal model is no longer required to explain the Mo concentration of the BSE if its abundance is in fact much higher, and similar to the values for ultramafic xenoliths.

Description: This study reports Mo isotopic compositions for fifty-two Palaeozoic granitic rocks with contrasting source affinities (A-, I- and S-type) from the Lachlan Fold Belt (LFB) and the New England Batholith (NEB), both in SE Australia, and three compositionally zoned plutons (Loch Doon, Criffell, and Fleet) located in the Southern Uplands of Scotland. The results show relatively large variations in δ98Mo for igneous rocks ranging from −1.73‰ to 0.59‰ with significant overlaps between different types. No relationships between δ98Mo and δ18O or ASI (Alumina Saturation Index) are observed, indicating that Mo isotopes do not clearly distinguish igneous vs. sedimentary source types. Instead, effects of igneous processes, source mixing, regional geology, as well as hydrothermal activity control the Mo isotope compositions in these granites. It is found that Mo is mainly accommodated in biotite and to a lesser extent in hornblende. Hornblende and Fe3+-rich minerals may preferentially incorporate light isotopes, as reflected by negative correlations between δ98Mo and K/Rb and [Fe2O3]. There is a positive correlation between initial 87Sr/86Sr and δ98Mo in I-type granitic rocks, reflecting the admixing of material from isotopically distinct sources. Granitic rocks from Scotland and Australia display strikingly similar curvilinear trends in δ98Mo vs. initial 87Sr/86Sr despite the differing regional geology. Localized hydrothermal effects can result in low δ98Mo in granite, as seen in three samples from Loch Doon and Criffell which have anomalously light δ98Mo of 〈−1‰. Based on this study, an estimate of δ98Mo = 0.14 ± 0.07‰ (95% s.e.) for the Phanerozoic upper crust is proposed. This is slightly heavier than basalts indicating an isotopically light lower crust and/or a systematic change to the crust resulting from subduction of isotopically light dehydrated slab and/or pelagic sediment over time.

Description: We present a double-spike technique for precise determination of mass-dependent fractionation of tungsten (W) stable isotopes. Instrumental mass bias effects and isotope fractionation during W separation are corrected for by means of a W-180-W-183 double-spike added prior to sample dissolution. The separation of W from the matrix is achieved via three-step anion-exchange chromatography. Tungsten stable isotopic compositions were determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Results are expressed relative to the NIST SRM 3136 W standard as the permil difference in W-186/W-184 (delta W-186). The external reproducibility of the NIST SRM 3163 W standard is +/- 0.05 parts per thousand with an average composition of -0.01 parts per thousand on W-186/W-184 (2s.d., n = 171). Tungsten stable isotope compositions for USGS standard reference materials are as follows: AGV-2 (andesite; delta W-186 +/- 0.18 +/- 0.05 parts per thousand, 2s.d., n = 6), SDC-1 (mica schist; delta W-186 = 0.36 +/- 0.05 parts per thousand, 2s.d., n = 6), SDO-1 (shale; delta W-186 = 0.26 +/- 0.06 parts per thousand, 2s.d., n = 6), and manganese nodules NOD-A-1 (delta W-186 = 0.07 +/- 0.05 parts per thousand, 2s.d., n = 10) and NOD-P-1 (delta W-186 = 0.31 +/- 0.04 parts per thousand, 2s.d., n = 7). The long-term external reproducibility (2s.d.) for these rock standards is +/- 0.05 parts per thousand.

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.