Description: We measured the chemical composition of 100 samples from the 250-m sediment sequence retrieved from Ocean Drilling Program Site 1256 in the Guatemala Basin using a newly developed microwave-assisted acid digestion protocol followed by inductively coupled plasma–atomic emission spectroscopy (ICP-AES) analysis. We compared these data gathered onshore to the results from the flux fusion prepared samples analyzed by shipboard ICP-AES during the leg and published in the Leg 206 Initial Reports volume, as well as to 35 randomly selected samples that were prepared by flux fusion at Boston University and analyzed by ICP-AES. Comparison of the newly developed acid digestion protocol to shore-based flux fusion demonstrates that the microwave-assisted acid technique yields a complete digestion, and because this procedure includes boric acid, it is safe for use with HF acid as boric acid neutralizes excess HF. The precision for nearly all elements in shore-based acid digestions is better than 3% of the measured values, including for elements such as Ni, Cr, and V, which are typically difficult to measure in biogenic-rich sediments. The shore-based flux fusions, while better than shipboard reported precision values (as expected), has precision better than 3% of their respective measured values for all major elements (Si, Al, Ti, Fe, Mn, Ca, Mg, Na, and K) and several trace elements (Ba and Sr). Results for P, Cr, Ni, V, Sc, and Zr are better than 5% of their measured values. Not only does the newly developed acid digestion provide better analytical results than the typical flux fusion method, the shore-based acid procedure also exhibits downhole lithologic and chemical characteristics similar to the shipboard flux fusion prepared results. These results confirm that the current shipboard methods are adequate for first-order geochemical interpretations and that the microwave-assisted acid digestion holds great potential to be the primary technique of preparing sediments on future Integrated Ocean Drilling Program expeditions.

Description: Biological productivity in the modern equatorial Pacific Ocean, a region with high nutrients and low chlorophyll, is currently limited by the micronutrient Fe. In order to test whether Fe was limiting in the past and to identify potential pathways of Fe delivery that could drive Fe fertilization (i.e., dust delivery from eolian inputs vs. Fe supplied by the Equatorial Undercurrent), we chemically isolated the terrigenous material from sediment along a cross-equatorial transect in the central equatorial Pacific at 140°W and at Ocean Drilling Program Site 850 in the eastern equatorial Pacific. We quantified the contribution from each potential Fe-bearing terrigenous source using a suite of chemical- and isotopic discrimination strategies as well as multivariate statistical techniques. We find that the distribution of the terrigenous sources (i.e., Asian loess, South American ash, Papua New Guinea, and ocean island basalt) varies through time, latitude, and climate. Regardless of which method is used to determine accumulation rate, there also is no relationship between flux of any particular Fe source and climate. Moreover, there is no connection between a particular Fe source or pathway (eolian vs. Undercurrent) to total productivity during the Last Glacial Maximum, Pleistocene glacial episodes, and the Miocene "Biogenic Bloom". This would suggest an alternative process, such as an interoceanic reorganization of nutrient inventories, may be responsible for past changes in total export in the open ocean, rather than simply Fe supply from dust and/or Equatorial Undercurrent processes. Additionally, perhaps a change in Fe source or flux is related to a change in a particular component of the total productivity (e.g., the production of organic matter, calcium carbonate, or biogenic opal).

Description: We measured major and trace element concentrations in the operationally defined, chemically extracted, residual aluminosilicate component of sediment from Ocean Drilling Program Sites 1215 and 1256 in the central and eastern equatorial Pacific Ocean and found that this residual component contains volcanogenic and authigenic aluminosilicates in addition to inferred eolian material. While the residual component younger than 20 Ma from the central Pacific (ODP Site 1215) is similar compositionally to upper continental crust and suggests an increase in the delivery of Asian dust material since 20 Ma, the residual in sediment older than 20 Ma indicates significant amounts of volcanogenic and authigenic materials. Volcanogenic debris comprises as much as ~ 40% of the residual between 23-40 Ma, which coincides with the mid-Tertiary "ignimbrite flare-up" that occurred in much of western North America. The residual component extracted from the 50 Ma biogenic sediment reflects authigenic signatures (seawater-like negative cerium anomalies and elevated Fe/Si ratios). The previously interpreted increase in an andesitic detrital source in North Pacific locations may instead be authigenic material, presenting significant challenges for many paleoclimate proxies. Additionally, in the eastern Pacific (ODP Site 1256), the residual component contains ~70% of volcanogenic material, most likely originating from Central America, and also includes refractory barite. The ability to separately identify eolian, volcanogenic, and authigenic materials in the aluminosilicate component of pelagic sediment allows resolution, respectively, of the climatic, geologic, and chemical processes contributing to the paleoceanographic archive in this critical oceanic region.