Chemical element contents and speciations in bottom sediments from the Transpacific profile

The paper deals with regularities of distribution of iron, manganese, copper, nickel, and vanadium in interstitial waters from different lithofacies types of bottom sediments on the profile from the coast of Mexico to the Wake Atoll in the Pacific Ocean. With increasing distance from the shore and with transition from reduced coastal sediments to oxidized deep-sea red clays concentration of iron and manganese in the interstitial waters greatly decreases. Elevated concentration of dissolved iron (0.34 mg/l) was observed only in highly reduced terrigenous sediments from the shelf and continental slope of Mexico. The highest concentrations of manganese (13.2 mg/l) were measured in hemipelagic carbonate-siliceous-clayey sediments. Compared to Pacific seawater interstitial waters are enriched in Fe, Mn, Cu, Ni, V. Interstitial waters contain only from 0.000004 to 1.2% of total contents of these elements in bottom sediments.

(Table 1) Vertical turbulent eddy diffusivity of selected stations from the Nathaniel B. Palmer cruise NBP09-01

Dissolved iron (DFe) and total dissolvable Fe (TDFe) were measured in January-February 2009 in Pine Island Bay, as well as in the Pine Island and Amundsen polynyas (Amundsen Sea, Southern Ocean). Iron (Fe) has been shown to be a limiting nutrient for phytoplankton growth, even in the productive continental shelves surrounding the Antarctic continent. However, the polynyas of the Amundsen Sea harbor the highest concentrations of phytoplankton anywhere in Antarctica. Here we present data showing the likely sources of Fe that enable such a productive and long lasting phytoplankton bloom. Circumpolar Deep Water (CDW) flows over the bottom of the shelf into the Pine Island Bay where DFe and TDFe were observed to increase from 0.2 to 0.4 nM DFe and from 0.3-4.0 to 7-14 nM TDFe, respectively. At the southern end of Pine Island Bay, the CDW upwelled under the Pine Island Glacier, bringing nutrients (including Fe) to the surface and melting the base of the glacier. Concentrations of DFe in waters near the Pine Island Glacier and the more westward lying Crosson, Dotson, and Getz Ice Shelves varied between 0.40 and 1.31 nM, depending on the relative magnitude of upwelling, turbulent mixing, and melting. These values represent maximum concentrations since associated ligands (which increase the solubility of Fe in seawater) were saturated with Fe (Thuroczy et al., 2012, doi:10.1016/j.dsr2.2012.03.009). The TDFe concentrations were very high compared to what previously has been measured in the Southern Ocean, varying between 3 and 106 nM. In the Pine Island Polynya, macronutrients and DFe were consumed by the phytoplankton bloom and concentrations were very low. We calculate that atmospheric dust contributed < 1% of the Fe necessary to sustain the phytoplankton bloom, while vertical turbulent eddy diffusion from the sediment, sea ice melt, and upwelling contributed 1.0-3.8%, 0.7-2.9%, and 0.4-1.7%, respectively. The largest source was Fe input from the PIG, which could satisfy the total Fe demand by the phytoplankton bloom by lateral advection of Fe over a range of 150 km from the glacier. The role of TDFe as a phytoplankton nutrient remains unclear, perhaps representing an important indirect Fe source via dissolution and complexation by dissolved organic ligands (Gerringa et al., 2000, doi:10.1016/S0304-4203(99)00092-4; Borer et al., 2005, doi:10.1016/j.marchem.2004.08.006).

(Table 3) Stable isotope record of Cretaceous foraminifera from DSDP Hole 44-392A

Mid-Cretaceous (Barremian-Turonian) plankton preserved in deep-sea marl, organic-rich shale, and pelagic carbonate hold an important record of how the marine biosphere responded to short- and long-term changes in the ocean-climate system. Oceanic anoxic events (OAEs) were short-lived episodes of organic carbon burial that are distinguished by their widespread distribution as discrete beds of black shale and/or pronounced carbon isotopic excursions. OAE1a in the early Aptian (~120.5 Ma) and OAE2 at the Cenomanian/Turonian boundary (~93.5 Ma) were global in their distribution and associated with heightened marine productivity. OAE1b spans the Aptian/Albian boundary (~113-109 Ma) and represents a protracted interval of dysoxia with multiple discrete black shales across parts of Tethys (including Mexico), while OAE1d developed across eastern and western Tethys and in other locales during the latest Albian (~99.5 Ma). Mineralized plankton experienced accelerated rates of speciation and extinction at or near the major Cretaceous OAEs, and strontium isotopic evidence suggests a possible link to times of rapid oceanic plateau formation and/or increased rates of ridge crest volcanism. Elevated levels of trace metals in OAE1a and OAE2 strata suggest that marine productivity may have been facilitated by increased availability of dissolved iron. The association of plankton turnover and carbon isotopic excursions with each of the major OAEs, despite the variable geographic distribution of black shale accumulation, points to widespread changes in the ocean-climate system. Ocean crust production and hydrothermal activity increased in the late Aptian. Faster spreading rates [and/or increased ridge length] drove a long-term (Albian-early Turonian) rise in sea level and CO2-induced global warming. Changes in ocean circulation, water column stratification, and nutrient partitioning lead to a reorganization of plankton community structure and widespread carbonate (chalk) deposition during the Late Cretaceous. We conclude that there were important linkages between submarine volcanism, plankton evolution, and the cycling of carbon through the marine biosphere.

Concentrations of rare earth elements in pore waters of IODP Holes 323-U1345A and 323-U1345B

We studied the diagenetic behavior of rare earth elements (REEs) in a highly productive passive margin setting of the Bering Sea Slope. Site U1345 was drilled during the Integrated Ocean Drilling Program Expedition 323 at a water depth of 1008 m currently in the center of an oxygen minimum zone. Pore water concentrations of fourteen REEs were determined down to ~ 140 meters below the seafloor (mbsf). The REE concentrations were higher in the pore water than the deep seawater, indicating that there was significant liberation from the sediments during diagenesis. There was a major peak at ~ 10 mbsf that was more pronounced for the heavy REE (HREE); this peak occurred below the sulfate-methane transition zone (6.3 mbsf) and coincided with high concentrations of dissolved iron and manganese. At ~ 2 mbsf, there was a minor peak in REE and Mn contents. Below ~ 40 mbsf, the REE concentration profiles remained constant. The Ce anomaly was insignificant and relatively constant (PAAS-normalized Ce/Ce = 1.1 ± 0.2) throughout the depth profile, showing that the Ce depleted in seawater was restored in the pore water. HREE-enrichment was observed over the entire 140 m except for the upper ~ 1 m, where a middle REE (MREE)-bulge was apparent. REE release in shallow depths (2-4 mbsf) is attributed to the release of light REEs (LREEs) and MREEs during the organoclastic reduction of Mn oxides in anoxic sediments. The high HREE concentrations observed at ~ 10 mbsf can be attributed to the reduction of Fe and Mn minerals tied to anaerobic oxidation of methane or, less significantly, to ferromagnesian silicate mineral weathering. The upward diffusion flux across the sediment-water interface was between 3 (for Tm) and 290 (for Ce) pmol/m**2/y.