Locations of geochemical samples and tephra from ODP Site 181-1123

Approximately one thousand sediment samples from ODP Site 1123 on the Chatham Rise, east of New Zealand, have been examined for inorganic elemental concentrations. ODP 1123 provides a record of sediment drift deposition under the Deep Western Boundary Current, the main inflow of deep water to the Pacific Ocean since the Early Oligocene, though a major hiatus spans the late Early Oligocene to the Early Miocene. Normalisation of the elemental concentrations by aluminium was used to allow for the effects of variable carbonate dilution. The elemental ratios were used as proxies for sediment composition and as palaeoceanographic indices. The samples were collected at a resolution designed to sample adequately any variation in elemental ratios at the scale of the Milankovitch orbital cycles. The sampled intervals span the Early Oligocene, Early Miocene, mid-Miocene and Late Pleistocene to Recent. Anomalous Si/Al, K/Al, Ti/Al values in the upper Pleistocene section, often associated with horizons of low carbonate, are attributed to tephras derived from North Island. Not all of the tephras detected geochemically had been detected visually in the cores. A total of 37 tephra events between 1.17 Ma BP and the present are recognised based on this and the shipboard investigations. The tephra events cluster at intervals of approximately 326 000 years (326 ka) perhaps due to variations in eruption frequency on North Island and/or to variations in the regional palaeowind intensity and direction. In the Late Pleistocene to Recent P/Al (inferred nutrient availability), percent calcium carbonate (%CaCO3) and Ba/Al (inferred productivity) varied regularly at a period of 40 000 years with these factors lagging minimum global ice volumes (interglacials). During the mid-Miocene CaCO3, Ba/Al, P/Al and Si/Al all gradually increased with %CaCO3 and P/Al showing regular 138 000-yr cyclicity and Ba/Al showing 44-ka cyclicity. Inferred productivity (Ba/Al) may have been rising in association with increasing nutrient availability (P/Al) at the same time as increased vigour of the Deep Western Boundary Current that was connected to a period of rapid ice-sheet growth in Antarctica. In the Early Miocene P/Al and Si/Al were much higher than subsequently and both %CaCO3 and P/Al exhibited 131 000-yr cycles. By far the highest nutrient levels and inferred productivity at this site apparently occurred during the Early Oligocene as revealed by long-term changes in P/Al and Si/Al. A progressive rise in K/Al, but stable Ti/Al from the Early Oligocene to the Recent probably indicates increased proportions of illite in the clay mineral fraction of the drift sediments caused by increased flux of debris from the Southern Alps.

Sequential variation of carbonate cycles in South Atlantic DSDP locations

We report well-dated Late Cretaceous and Early Tertiary precessional climatic cycles, recorded by rhythmic carbonate maxima and minima in South Atlantic deep sea sites. Spectral analyses of digitized sediment color, a suitable carbonate proxy, show prominent regularities in the spacing marl-carbonate beds. Magnetostratigraphic dating over a number of magnetic chrons constrains the duration of the cycles, which can be detected over at least 20 Myr of sedimentation at 7 coring locations. Their mean absolute period of 23.5 +/- 4.4kyr agrees closely with the predicted late Cretaceous precessional period of 20.8 kyr. Because they can be matched to a physical forcing mechanism with a known repeat time, the cycles offer a new high-resolution tool to measure rates of climate change before and after the Cretaceous-Tertiary (K/T) boundary. From counts of carbonate cycles, we derive the position of the K/T boundary within C29R at 350 kyr after the base of the reversal. The constancy of cycle thickness (linearly related to sedimentation rate) and amplitude up to the "boundary clay" does not give evidence for climate instability preceding the boundary. Orbital chronometry records a step-function decrease in sediment accumulation rate at the Cretaceous-Tertiary boundary that is consistent with a geologically instantaneous event.

Direct visualization of solute locations in laboratory ice samples, links to videos

Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air-ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, similar research has not identified solute locations in laboratory samples, nor the possible factors controlling solute segregation. To address this, we examined solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or Rose Bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (~2 µm). Freezing solutions in plastic versus glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with Rose Bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results.

Revised composite depth scale, Fe content and orbital tuning of Middle Eocene Climate Optimum samples from ODP Site 207-1260

A high-resolution stratigraphy is essential toward deciphering climate variability in detail and understanding causality arguments of events in earth history. Because the highly dynamic middle to late Eocene provides a suitable testing ground for carbon cycle models for a waning warm world, an accurate time scale is needed to decode climate-driving mechanisms. Here we present new results from ODP Site 1260 (Leg 207) which covers a unique expanded middle Eocene section (magnetochrons C18r to C20r, late Lutetian to early Bartonian) of the tropical western Atlantic including the chron C19r transient hyperthermal event and the Middle Eocene Climate Optimum (MECO). To establish a detailed cyclostratigraphy we acquired a distinctive iron intensity records by XRF scanning Site 1260 cores. We revise the shipboard composite section, establish a cyclostratigraphy and use the exceptional eccentricity modulated precession cycles for orbital tuning. The new astrochronology revises the age of magnetic polarity chrons C19n to C20n, validates the position of very long eccentricity minima at 40.2 and 43.0 Ma in the orbital solutions, and extends the Astronomically Tuned Geological Time Scale back to 44 Ma. For the first time the new data provide clear evidence for an orbital pacing of the chron C19r event and a likely involvement of the very long eccentricity cycle contributing to the evolution of the MECO.

Sample locations, CTD data, mean spring and annual temperatures and salinities from World Ocean Atlas (WOA, 2001), and ICP-OES Mg/Ca data

Due to its strong gradient in salinity and small temperature gradient the Mediterranean provides an ideal setting to study the impact of salinity on the incorporation of Mg into foraminiferal tests. We have investigated tests of Globorotalia inflata and Globigerina bulloides in plankton tow and core top samples from the Western Mediterranean using ICP-OES for bulk analyses and LA-ICP-MS for analyses of individual chambers in single specimens. Mg/Ca observed in G. inflata are consistent with existing calibrations, whereas G. bulloides had significantly higher Mg/Ca than predicted, particularly in core top samples from the easterly stations. Scanning Electron Microscopy and Laser Ablation ICP-MS revealed secondary overgrowths on some tests, which could explain the observed high core top Mg/Ca. We suggest that the Mediterranean intermediate and deep water supersaturated with respect to calcite cause these overgrowths and therefore increased bulk Mg/Ca. However, the different species are influenced by diagenesis to different degrees probably due to different test morphologies. Our results provide new perspectives on reported anomalously high Mg/Ca in sedimentary foraminifera and the applicability of the Mg/Ca paleothermometry in high salinity settings, by showing that (1) part of the signal is generated by precipitation of inorganic calcite on the foraminifer test due to increased calcite saturation state of the water and (2) species with high surface-to-volume shell surfaces are potentially more affected by secondary Mg-rich calcite encrustation.

Carbonate concentrations of ODP Leg 115 samples

We measured carbonate concentrations in Pleistocene and Pliocene sediments deposited at Sites 709, 710, and 711. Carbonate concentrations exhibit low-amplitude, long-wave length (300-400 k.y. period) variations at the shallowest sites (709 and 710). Before 2.47 Ma, all three sites exhibit higher frequency (100 k.y. period) variations. The deepest site (711) exhibited low-amplitude variations and very low concentrations up to the Gauss/Matuyama magnetic reversal (2.47 Ma), then concentrations abruptly increased. After 2.47 Ma, carbonate concentrations at Site 711 exhibited the same periodic changes as at Site 709. Although a long wave-length periodicity (260-280 k.y.) occurs at these sites after 2.47 Ma, the 100 k.y. period is absent. The dominant periods observed in these data are those found in the eccentricity component of the earth's orbital geometry. Estimates of carbonate accumulation at Sites 709 and 710 document that surface-water productivity decreased near the Gauss/Matuyama magnetic reversal whereas accumulation at Site 711 increased. These results indicate that the rate of carbonate preservation in the deep Indian Ocean increased at that time. This increase in preservation may have re- sulted from a decrease in the production rate of carbonate in tropical oceans of the world. Carbonate accumulation esti- mated from sediments in shallow locations (~3000-3800 m) of the Atlantic and Pacific oceans also indicates that carbonate production decreased at this time. A consequence of lowered surface-water productivity is increased carbonate ion concentration of the deep ocean and better preservation of carbonate on the seafloor.

Stable isotope record of benthic foraminifera in late Pleistocene sediments

Variations in the contribution of North Atlantic Deep Water (NADW), relative to North Pacific Deep Water (NPDW), to the Southern Ocean, are assessed by comparing delta13C records from the mid-depth North Atlantic, deep Southern Ocean, and deep equatorial Pacific Ocean. In general, the relative contribution of NADW was greater during interglaciations than glaciations of the past 550,000 years. An increase in the NADW flux to the Southern Ocean since the last glaciation was proposed to have resulted in higher atmospheric CO2 in the Holocene (Broecker and Peng, 1989, doi:10.1029/GB003i003p00215). Glacial-interglacial variations in the proportion of NADW in the Southern Ocean may have also influenced atmospheric CO2 levels over the past 550,000 years. The greatest relative flux of NADW to the Southern Ocean occurred during interglacial stage 11. Faunal data suggest that the North Atlantic polar front and southern Indian Ocean subtropical convergence zone were located farthest poleward during stage 11. Warmth in these locations and a strong southward flux of NADW during stage 11 may be causally linked by the NADW formation process/warm water return route (Gordon, 1986, doi:10.1029/JC091iC04p05037). Time series analysis indicates that delta13C variations in the deep Southern Ocean occur at the same frequencies as the Earth's orbital variations and are coherent and in phase with delta18O. At most, 50% of the glacial-interglacial delta13C amplitude in the Southern Ocean is due changes in the contribution of NADW. The remainder is probably due to mean ocean delta13C changes.