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.

Pliocene and Pleistocene abundance of siliceous microfossil assemblages in ODP Leg 127 sites

A close examination of the siliceous microfossil assemblages from the sediments of ODP Leg 127, Japan Sea Sites 794, 795, and 797, reveals that upper Pliocene and Pleistocene assemblages have been subjected to more dissolution than have lower Pliocene assemblages. This conclusion is based on semiquantitative observations of samples processed for diatoms and radiolarians. Although preservation of opaline microfossils in some upper Pliocene and Pleistocene samples is better than others, in general, the poorly preserved state of these assemblages supports the notion that opal dissolution, in response to lowered productivity, is responsible for the paucity of siliceous microfossils in upper Pliocene and Pleistocene sediments. The lithological transition from diatomaceous oozes to silts and clays corresponds to a change between dominantly well preserved to more poorly preserved siliceous assemblages, and is termed the late Pliocene Japan Sea opal dissolution transition zone (ODTZ). The base of the ODTZ is defined as the uppermost occurrence of high abundances of moderately to well preserved valves of the diatom Coscinodiscus marginatus. The dissolution transition zone is characterized by partially dissolved refractory assemblages of radiolarians, the presence of C. marginatus girdles, C. marginatus fragments, siliceous sponge spicules, and a general decrease in weakly silicified, less solution resistant diatoms upward in the section. The top of the dissolution transition zone marks the level where whole C. marginatus valves and C. marginatus fragments are no longer present in significant numbers. Dissolution of the late Pliocene and Pleistocene opaline assemblages is attributed mainly to changes in paleoceanographic circulation patterns and decreased nutrient (dissolved silicon) contents of the water column, and possibly dissolution at the sediment/water interface, rather than to post-depositional dissolution or diagenesis. We suggest that the transition from silica-rich to silica-poor conditions in the Japan Sea was due to fluctuations of deep-water exchange with the Pacific through the Tsugaru Strait between 2.9 and 2.3 Ma.