(Table A1) Diatom isotope measurements from ODP Hole 145-882A

In comparison to other sectors of the marine system, the palaeoceanography of the subarctic North Pacific Ocean is poorly constrained. New diatom isotope records of d13C, d18O, d30Si (d13Cdiatom, d18Odiatom, and d30Sidiatom) are presented alongside existing geochemical and isotope records to document changes in photic zone conditions, including nutrient supply and the efficiency of the soft-tissue biological pump, between Marine Isotope Stage (MIS) 4 and MIS 5e. Peaks in opal productivity in MIS 5b/c and MIS 5e are both associated with the breakdown of the regional halocline stratification and increased nutrient supply to the photic zone. Whereas the MIS 5e peak is associated with low rates of nutrient utilisation, the MIS 5b/c peak is associated with significantly higher rates of nutrient utilisation. Both peaks, together with other smaller increases in productivity in MIS 4 and 5a, culminate with a significant increase in freshwater input which strengthens/re-establishes the halocline and limits further upwelling of sub-surface waters to the photic zone. Whilst d30Sidiatom and previously published records of diatom d15N (d15Ndiatom) (Brunelle et al., 2007, 2010) show similar trends until the latter half of MIS 5a, the records become anti-correlated after this juncture and into MIS 4, suggesting a possible change in photic zone state such as may occur with a shift to iron or silicon limitation.

Pliocene sediment and silicon isotope record of ODP Site 145-882

Increases in the low-field mass-specific magnetic susceptibility (chi), dropstones and the terrigenous sediment component from Ocean Drilling Program (ODP) Site 882 (~45°N) have been interpreted to indicate a major onset of ice-rafting to the sub-Arctic northwest Pacific Ocean during marine isotope stage (MIS) G6 (from ~2.75 Ma). In contrast, studies of the terrigenous content of sediments cored downwind of ODP Site 882 indicate that dust and disseminated volcanic ash deposition in the sub-Arctic Pacific increased markedly during MIS G6. To investigate the relative contribution of dust, volcanic ash and ice rafting to the Pliocene chi increase, we present new high-resolution environmental magnetic and ice-rafted debris records from ODP Sites 882 and 885. Our results demonstrate that the chi increase at both sites across MIS G6 is predominantly controlled by a previously overlooked mixture of aeolian dust and volcanic ash. Our findings call into question the reliability of chi as a proxy for ice-rafting to the North Pacific. They also highlight a previously undocumented link between iron fertilisation and biogeochemical cycling in the North Pacific at a key stage during intensification of late Pliocene northern hemisphere glaciation.

Pacific Neogene carbonate accumulation rates

I have compiled CaCO3 mass accumulation rates (MARs) for the period 0-25 Ma for 144 Deep Sea Drilling Project and Ocean Drilling Program drill sites in the Pacific in order to investigate the history of CaCO3 burial in the world's largest ocean basin. This is the first synthesis of data since the beginning of the Ocean Drilling Program. Sedimentation rates, CaCO3 contents, and bulk density were estimated for 0.5 Myr time intervals from 0 to 14 Ma and for 1 Myr time intervals from 14 to 25 Ma using mostly data from Initial Reports volumes. There is surprisingly little coherence between CaCO3 MAR time series from different Pacific regions, although regional patterns exist. A transition from high to low CaCO3 MAR from 23-20 Ma is the only event common to the entire Pacific Ocean. This event is found worldwide. The most likely cause of lowered pelagic carbonate burial is a rising sea-level trend in the early Miocene. The central and eastern equatorial Pacific is the only region with adequate drill site coverage to study carbonate compensation depth (CCD) changes in detail for the entire Neogene. The latitude-dependent decrease in CaCO3 production away from the equator is an important defining factor of the regional CCD, which shallows away from the equatorial region. Examination of latitudinal transects across the equatorial region is a useful way to separate the effects of changes in carbonate production ('productivity') from changes in bottom water chemistry ('dissolution') upon carbonate burial.

Age determination of ODP Hole 145-887

Atmospheric carbon dioxide concentrations were significantly lower during glacial periods than during intervening interglacial periods, but the mechanisms responsible for this difference remain uncertain. Many recent explanations call on greater carbon storage in a poorly ventilated deep ocean during glacial periods (Trancois et al., 1997, doi:10.1038/40073; Toggweiler, 1999, doi:10.1029/1999PA900033; Stephens and Keeling, 2000, doi:10.1038/35004556; Marchitto et al., 2007, doi:10.1126/science.1138679; Sigman and Boyle, 2000, doi:10.1038/35038000), but direct evidence regarding the ventilation and respired carbon content of the glacial deep ocean is sparse and often equivocal (Broecker et al., 2004, doi:10.1126/science.1102293). Here we present sedimentary geochemical records from sites spanning the deep subarctic Pacific that -together with previously published results (Keigwin, 1998, doi:10.1029/98PA00874)- show that a poorly ventilated water mass containing a high concentration of respired carbon dioxide occupied the North Pacific abyss during the Last Glacial Maximum. Despite an inferred increase in deep Southern Ocean ventilation during the first step of the deglaciation (18,000-15,000 years ago) (Marchitto et al., 2007, doi:10.1126/science.1138679; Monnin et al., 2001, doi:10.1126/science.291.5501.112), we find no evidence for improved ventilation in the abyssal subarctic Pacific until a rapid transition ~14,600 years ago: this change was accompanied by an acceleration of export production from the surface waters above but only a small increase in atmospheric carbon dioxide concentration (Monnin et al., 2001, doi:10.1126/science.291.5501.112). We speculate that these changes were mechanistically linked to a roughly coeval increase in deep water formation in the North Atlantic (Robinson et al., 2005, doi:10.1126/science.1114832; Skinner nd Shackleton, 2004, doi:10.1029/2003PA000983; McManus et al., 2004, doi:10.1038/nature02494), which flushed respired carbon dioxide from northern abyssal waters, but also increased the supply of nutrients to the upper ocean, leading to greater carbon dioxide sequestration at mid-depths and stalling the rise of atmospheric carbon dioxide concentrations. Our findings are qualitatively consistent with hypotheses invoking a deglacial flushing of respired carbon dioxide from an isolated, deep ocean reservoir periods (Trancois et al., 1997, doi:10.1038/40073; Toggweiler, 1999, doi:10.1029/1999PA900033; Stephens and Keeling, 2000, doi:10.1038/35004556; Marchitto et al., 2007, doi:10.1126/science.1138679; Sigman and Boyle, 2000, doi:10.1038/35038000; Boyle, 1988, doi:10.1038/331055a0), but suggest that the reservoir may have been released in stages, as vigorous deep water ventilation switched between North Atlantic and Southern Ocean source regions.

Nd, Sm and carbon isotopic data for samples from ODP Legs 115, 145, 171, and 207

Late Cretaceous fish debris from Demerara Rise exhibits a dramatic positive excursion of 8 e-Nd units during ocean anoxic event 2 (OAE2) that is superimposed on extremely low e-Nd(t) values (-14 to -16.5) observed throughout the rest of the studied interval. The OAE2 e-Nd excursion is the largest yet documented in marine sediments, and the majority of the shift is estimated to have occurred over <20 k.y. Low background e-Nd values on Demerara Rise are explained as the Nd isotopic signature of the South American craton, whereas eruptions of the Caribbean large igneous province or enhanced mixing of intermediate waters in the North Atlantic could have caused the excursion.