(Tables 4-5, page 160) REE contents in ferromanganese concretions from the Gulf of Bothnia and the Barents Sea

Ferromanganese concretions from the Svalbard shelf in the Barents Sea show slightly convex shale-normalized REE patterns with no Eu anomalies. Concretions from the Gulf of Bothnia, northern part of the Baltic Sea, exhibit an enrichment of light REE and negative Eu anomalies. This difference is interpreted as a consequence of different conveyor mechanisms of the REE to the sediment. It is suggested that dissolving biogenic debris contributes to the convex pattern obtained in the Barents Sea, whereas an inorganic suspended fraction with scavenged REE is the main carrier in the Gulf of Bothnia. During oxic diagenesis in the sediment, the scavenged REE are set free into the porewater and contribute to the distribution pattern in concretions found in the Gulf of Bothnia. Small Mn-rich spheroidal concretions are enriched two to five times in REE compared to average shale, whereas Mn-poor flat concretions are low in REE. Specific surface area of the concretion and the depth of burial in the oxidized surface sediment are two factors that strongly affect the enrichment of the REE. Weak Ce anomalies are present in the analysed concretions and a redox level dependence is seen.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.