Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

(Table 2) Trace metal concentrations in ODP Hole 169-1033B

We measured the concentrations of redox-sensitive trace metals (Mn, V, Mo, U, Cd and Re) in sediments from ODP Leg 169S Hole 1033B in Saanich Inlet, British Columbia, to determine changes in redox conditions associated with the onset of laminated sediments at ~12.5 kyr. The most striking result is a large peak in authigenic Re along with detrital levels of Mo at the glacial terrigenous clay-diatomaceous sediment transition. In contrast, the underlying glacial terrigenous clay, which extends throughout the bottom section of the core, is chemically similar to detrital concentrations, either Cowichan River particulates or average shale values. These data suggest a period of oxic bottom waters but reducing pore-waters. This could be due to the dramatic transformation of Saanich Inlet during the late deglaciation from an open bay to an inlet, which restricted circulation and slowed bottom water oxygen renewal. A peak and gradual increase in authigenic Mn in younger sediments subsequent to the Re peak suggests that increasingly oxic conditions followed the authigenic enrichment in Re. These conditions could be connected to the Younger Dryas cooling period, which was coincident with an increase in well oxygenated upwelled waters on the west coast of North America that form the bottom waters of Saanich Inlet. Metal concentrations in a gray clay bed (~11 kyr) are similar to their concentrations in the glacial terrigenous clay, implying that they have a common source. Authigenic enrichments of Re with little authigenic Mo and Cd suggest that before the deposition of this bed, bottom waters were oxic and pore-water oxygen was consumed in the top centimeter or less. Laminations above the clay layer suggest anoxic conditions, which are also indicated by higher authigenic Mo and Cd and slightly lower Re/Mo ratios in these sediments. The basin remained mostly anoxic after the gray clay was emplaced, as seen by continuous authigenic enrichment of the redox-sensitive trace metals. These results are consistent with increased stratification of the water column, brought about by an influx of fresh water to the basin by a large flood.

Total organic carbon, metal concentrations and metal and aluminium ratios in bulk sediment from the ODP sample 169-1033B-4H-4,54-74

Holocene laminated sediments in Saanich Inlet, British Columbia, are interrupted by frequent, non-laminated, massive layers. These layers may be debris flows released by earthquakes or bioturbated sediments deposited during periods of relatively high bottom water oxygen concentration and/or low surface productivity, or both. We determined the organic carbon content and the concentration of a suite of redox-sensitive metals in bulk sediments at approximately 1-cm resolution across a laminated-massive-laminated interval (ODP Leg 169S Sample 1033B-4H-4,54-74), to determine the redox conditions under which the massive layer was deposited. Our results indicate that this massive interval was deposited under anoxic bottom waters. Manganese/Al ratios are consistently low throughout the massive section, while Mo/Al, Cd/Al, Re/Al, and U/Al ratios are enriched relative to their metal/Al ratios in detrital material (represented by Cowichan River suspended sediments). The concentration of organic carbon in the lower portion of the massive layer is higher than in the upper portion, which has a concentration similar to that in the overlying and underlying laminated sediments. Well-defined peaks in Mo/Al, Cd/Al, and Re/Al and a broad peak in U/Al occur in the lower portion of the massive layer. The positions of the Cd/Al, Re/Al, and Mo/Al peaks, as well as the increase in organic carbon content with depth in the massive layer, are best explained by a process of diagenetic redistribution of metals that occurred after the massive layer was emplaced.

Beryllium, neodymium and metal composition of ODP Leg 194 sites and survey sites crusts

Be and Nd isotope compositions and metal concentrations (Mn, Fe, Co, Ni, and Cu) of surface and subsurface ferromanganese hardground crusts from Ocean Drilling Program Leg 194 Marion Plateau Sites 1194 and 1196 provide new insights into the crusts' genesis, growth rates, and ages. Metal compositions indicate that the hardgrounds, which have grown on erosional surfaces in water depths of <400 m because of strong bottom currents, are not pure hydrogenetic precipitates. Nevertheless, the ratios between cosmogenic 10Be and stable 9Be in hardgrounds from the present-day seafloor at Site 1196 between 1 x 10**-7 and 1.5 x 10**-7 are within the range of values expected for Pacific seawater, which shows that the hardgrounds recorded the isotope composition of ambient seawater. This is also confirmed by their Nd isotope composition (epsilon Nd between -3 and 0). The 10Be/9Be ratios in the up to 30-mm-thick and partly laminated hardgrounds do not show a decrease with depth, which suggests high growth rates on the present-day seafloor. The subsurface crust at Site 1194 (117 m below the seafloor) grew during a sedimentation hiatus, when bottom currents in the late Miocene prevented sediment accumulation on the carbonate platform during a sea level lowstand. The age of 8.65 ± 0.50 Ma for this crust obtained from 10Be-based dating agrees well with the combined seismostratigraphic and biostratigraphic evidence, which suggests an age for the hiatus between 7.7 and 11.8 Ma.