Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Additional CaCO3 measurements from IODP Site 306-U1313

We present further %CaCO3 data from Site U1313 across the Pliocene-Pleistocene intensification of Northern Hemisphere glaciation. This data was measured on the U1313 secondary splice. We also present tie points between the primary and secondary splice for this interval based on graphical tuning of L* (sediment lightness).

CaCO3, foraminifer fragmentation, benthic carbon isotopes, coarse lithic counts and radiogenic isotopes (Sr, Nd, Pb) of the Pliocene and earliest Pleistocene terrigenous component (3.3-2.4 Ma) of IODP Site 306-U1313

We present Plio-Pleistocene records of sediment color, %CaCO3, foraminifer fragmentation, benthic carbon isotopes (d13C) and radiogenic isotopes (Sr, Nd, Pb) of the terrigenous component from IODP Site U1313, a reoccupation of benchmark subtropical North Atlantic Ocean DSDP Site 607. We show that (inter)glacial cycles in sediment color and %CaCO3 pre-date major northern hemisphere glaciation and are unambiguously and consistently correlated to benthic oxygen isotopes back to 3.3 million years ago (Ma) and intermittently so probably back to the Miocene/Pliocene boundary. We show these lithological cycles to be driven by enhanced glacial fluxes of terrigenous material (eolian dust), not carbonate dissolution (the classic interpretation). Our radiogenic isotope data indicate a North American source for this dust (~3.3-2.4 Ma) in keeping with the interpreted source of terrestrial plant wax-derived biomarkers deposited at Site U1313. Yet our data indicate a mid latitude provenance regardless of (inter)glacial state, a finding that is inconsistent with the biomarker-inferred importance of glaciogenic mechanisms of dust production and transport. Moreover, we find that the relation between the biomarker and lithogenic components of dust accumulation is distinctly non-linear. Both records show a jump in glacial rates of accumulation from Marine Isotope Stage, MIS, G6 (2.72 Ma) onwards but the amplitude of this signal is about 3-8 times greater for biomarkers than for dust and particularly extreme during MIS 100 (2.52 Ma). We conclude that North America shifted abruptly to a distinctly more arid glacial regime from MIS G6, but major shifts in glacial North American vegetation biomes and regional wind fields (exacerbated by the growth of a large Laurentide Ice Sheet during MIS 100) likely explain amplification of this signal in the biomarker records. Our findings are consistent with wetter-than-modern reconstructions of North American continental climate under the warm high CO2 conditions of the Early Pliocene but contrast with most model predictions for the response of the hydrological cycle to anthropogenic warming over the coming 50 years (poleward expansion of the subtropical dry zones).

Chemical composition of DSDP cherts and associated host sediments

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO2 concentration in chert, often with final SiO2 >=98 wt%. This contrast in SiO2 (and Si/Al) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO2 concentrations and Si/Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO2, construct a chert composition which is essentially identical to observed SiO2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO2 concentration contrast seems caused by biogenic SiO2 dissolution and transport from the local adjacent host sediment and subsequent SiO2 reprecipitation in the chert. Along with SiO2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO/Al2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce/Ce* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu/Eu* decreases slightly during formation of DSDP chert. Normative La/Yb is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE/Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.