(Table 2) Age determination of sediment cores from the continental shelf of Mac Roberston Land, East Antarctica

Geochemical records are presented for five sediment cores from basins on the continental shelf of Mac. Robertson Land, East Antarctica. The cores contain 2-4 m thick sequences of hemipelagic, siliceous mud and ooze (SMO) deposited under seasonally open marine conditions. The inner and middle shelf SMO sequences are massive dark olive green material, whereas the outer shelf SMO sequences are dark olive material interspersed with light olive green layers ~1-10 cm thick. The biogenic material is dominated by marine diatoms including Fragilariopsis curta, Fragilariopsis cylindrus, and Chaetoceros spp. in the dark-colored SMO and Corethron criophilum in the light-colored layers. Radiocarbon dates suggest that the cores provide continuous accumulation records extending from < 1 kyr before present (B.P.) back as far as 4-15 kyr B.P., with estimated accumulation rates of 0.07-5 mm/yr. The three core records from the middle and outer shelf suggest six episodes of increased accumulation of biogenic material at ~5.5 kyr B.P. (all three cores), 1, 2, and 6.2 kyr B.P. (two of the three cores), and 3.8 and 10.8 kyr B.P. (one core), most of which coincide with Corethron layers. We interpret these features as the result of enhanced diatom production over the outer shelf, possibly related to climatic warm periods. The absence of such features in the inner shelf core records is thought to reflect a relatively constant level of seasonal diatom production in adjacent waters maintained by a coastal polynya.

Stable isotope ratios on planktonic foraminifer N. pachyderma of surface sediments from the Arctic Ocean (Table 1)

Planktic foraminifers Neogloboquadrina pachyderma (sin.) from 87 eastern and central Arctic Ocean surface sediment samples were analyzed for stable oxygen and carbon isotope composition. Additional results from 52 stations were taken from the literature. The lateral distribution of delta18O (18O/16O) values in the Arctic Ocean reveals a pattern of roughly parallel, W-E stretching zones in the Eurasian Basin, each ~0.5 per mil wide on the delta18O scale. The low horizontal and vertical temperature variability in the Arctic halocline waters (0-100 m) suggests only little influence of temperature on the oxygen isotope distribution of N. pachyderma (sin.). The zone of maximum delta18O values of up to 3.8 per mil is situated in the southern Nansen Basin and relates to the tongue of saline (> 33%.) Atlantic waters entering the Arctic Ocean through the Fram Strait. delta18O values decrease both to the Barents Shelf and to the North Pole, in accordance with the decreasing salinities of the halocline waters. In the Nansen Basin, a strong N-S delta18O gradient is in contrast with a relatively low salinity change and suggests contributions from different freshwater sources, i.e. salinity reduction from sea ice meltwater in the south and from light isotope waters (meteoric precipitation and river-runoff) in the northern part of the basin. North of the Gakkel Ridge, delta18O and salinity gradients are in good accordance and suggest less influence of sea ice melting processes. The delta13C (13C/12C) values of N. pachyderma (sin.) from Arctic Ocean surface sediment samples are generally high (0.75-0.95 per mil). Lower values in the southern Eurasian Basin appear to be related to the intrusion of Atlantic waters. The high delta13C values are evidence for well ventilated surface waters. Because the perennial Arctic sea ice cover largely prevents atmosphere-ocean gas exchange, ventilation on the seasonally open shelves must be of major importance. Lack of delta13C gradients along the main routes of the ice drift from the Siberian shelves to the Fram Strait suggests that primary production (i.e. CO2 consumption) does probably not change the CO2 budget of the Arctic Ocean significantly.

(Table S1) Chronostratigraphic constrains for sediment core AND1-1B

Thirty years after oxygen isotope records from microfossils deposited in ocean sediments confirmed the hypothesis that variations in the Earth's orbital geometry control the ice ages (Hays et al., 1976, doi:10.1126/science.194.4270.1121), fundamental questions remain over the response of the Antarctic ice sheets to orbital cycles (Raymo and Huybers, 2008, doi:10.1038/nature06589). Furthermore, an understanding of the behaviour of the marine-based West Antarctic ice sheet (WAIS) during the 'warmer-than-present' early-Pliocene epoch (~5-3 Myr ago) is needed to better constrain the possible range of ice-sheet behaviour in the context of future global warming (Solomon et al., 2007). Here we present a marine glacial record from the upper 600 m of the AND-1B sediment core recovered from beneath the northwest part of the Ross ice shelf by the ANDRILL programme and demonstrate well-dated, ~40-kyr cyclic variations in ice-sheet extent linked to cycles in insolation influenced by changes in the Earth's axial tilt (obliquity) during the Pliocene. Our data provide direct evidence for orbitally induced oscillations in the WAIS, which periodically collapsed, resulting in a switch from grounded ice, or ice shelves, to open waters in the Ross embayment when planetary temperatures were up to ~3° C warmer than today ( Kim and Crowley, 2000, doi:10.1029/1999PA000459) and atmospheric CO2 concentration was as high as ~400 p.p.m.v. (van der Burgh et al., 1993, doi:10.1126/science.260.5115.1788, Raymo et al., 1996, doi:10.1016/0377-8398(95)00048-8). The evidence is consistent with a new ice-sheet/ice-shelf model (Pollard and DeConto, 2009, doi:10.1038/nature07809) that simulates fluctuations in Antarctic ice volume of up to +7 m in equivalent sea level associated with the loss of the WAIS and up to +3 m in equivalent sea level from the East Antarctic ice sheet, in response to ocean-induced melting paced by obliquity. During interglacial times, diatomaceous sediments indicate high surface-water productivity, minimal summer sea ice and air temperatures above freezing, suggesting an additional influence of surface melt (Huybers, 2006, doi:10.1126/science.1125249) under conditions of elevated CO2.

(Table 1) Iron and manganese speciations in surface layer bottom sediments of the Pacific Ocean

Distribution of iron and manganese speciations in ocean sediments of a section from the coast of Japan to the open Pacific Ocean is under consideration. Determinations of total iron, as well as of reactive iron contents and of total manganese, as well as of Mn4+ contents have been done. Significant increase of total Fe content in sediments from the coast to the pelagic zone occurs without noticeable increase in reactive Fe content. Presence of layers of volcanic and terrigenous coarse clastic material in clayey sediments results to sharp change in iron content. Manganese content increases from near coastal to pelagic sediments more than 10 times; oxidation degree of sediments also increases. There are three types of bottom sediments different by contents of iron and manganese forms: reduced, oxidized (red clay), and transitional. Content of total Fe is almost does not change with depth in sediments, content of reactive Fe increases in reduced sediments, and decreases in oxidized ones. Manganese content in red clay mass increases several times.

(Table, Appendix C) Metal content of nodules at Sea Scope stations based upon XRF analyses at the Ore Microscopy Laboratory, Washington State Unicersity, USA

New information on possible resource value of sea floor manganese nodule deposits in the eastern north Pacific has been obtained by a study of records and collections of the 1972 Sea Scope Expedition. Nodule abundance (percent of sea floor covered) varies greatly, according to photographs from eight stations and data from other sources. All estimates considered reliable are plotted on a map of the region. Similar maps show the average content of Ni, Cu, Mn and Co at 89 stations from which three or more nodules were analyzed. Variations in nodule metal content at each station are shown graphically in an appendix, where data on nodule sizes are also given. Results of new analyses of 420 nodules from 93 stations for mn, fe, ni, cu, CO, and zn are listed in another appendix. Relatively high Ni + Cu content is restricted chiefly to four groups of stations in the equatorial region, where group averages are 1.86, 1.99, 2.47, and 2.55 weight-percent. Prepared for United States Department of the Interior, Bureau of Mines. Grant no. GO284008-02-MAS. - NTIS PB82-142571.

(Table 1) Characteristics of marine snow and ice samples at Barrow, Alaska

We measured light absorption in 42 marine snow, sea ice, seawater, brine, and frost flower samples collected during the OASIS field campaign between February 27 and April 15, 2009. Samples represented multiple sites between landfast ice and open pack ice in coastal areas approximately 5 km west of Barrow, Alaska. The chromophores that are most commonly measured in snow, H2O2, NO3-, and NO2-, on average account for less than 1% of sunlight absorption in our samples. Instead, light absorption is dominated by unidentified "residual" species, likely organic compounds. Light absorption coefficients for the frost flowers on first-year sea ice are, on average, 40 times larger than values for terrestrial snow samples at Barrow, suggesting very large rates of photochemical reactions in frost flowers. For our marine samples the calculated rates of sunlight absorption and OH production from known chromophores are (0.1-1.4) x 10**14 (photons/cm**3/s) and (5-70) x 10**-12 (mol/L/s), respectively. Our residual spectra are similar to spectra of marine chromophoric dissolved organic matter (CDOM), suggesting that CDOM is the dominant chromophore in our samples. Based on our light absorption measurements we estimate dissolved organic carbon (DOC) concentrations in Barrow seawater and frost flowers as approximately 130 and 360 µM C, respectively. We expect that CDOM is a major source of OH in our marine samples, and it is likely to have other significant photochemistry as well.

(Table 1) Oxygen and carbon isotopes for planktonic foraminifers at DSDP Hole 64-480

During the cleaning of the HPC core surfaces from Hole 480 for photography, the material removed was conserved carefully in approximately 10 cm intervals (by K. Kelts); this material was made available to us in the hope that it would be possible to obtain oxygen isotope stratigraphy for the site. The samples were, of course, somewhat variable in size, but the majority were probably between 5 and 10 cm**3. Had this been a normal marine environment, such sample sizes would have contained abundant planktonic foraminifers together with a small number of benthics. However, this is clearly not the case, for many samples contained no foraminifers, whereas others contained more benthics than planktonics. Among the planktonic foraminifers the commonest species are Globigerina bulloides, Neogloboquadrina dutertrei, and N. pachyderma. A few samples contain a more normal fauna with Globigerinoides spp. and occasional Globorotalia spp. Sample 480-3-3, 20-30 cm contained Globigerina rubescens, isolated specimens of which were noted in a few other samples in Cores 3,4, and 5. This is a particularly solution-sensitive species; in the open Pacific it is only found widely distributed at horizons of exceptionally low carbonate dissolution, such as. the last glacial-to-interglacial transition.

(Table 1) Age determination of sediment core BC5, Golf of Lion

Hitherto unknown abundance peaks of left coiling (l.c.) Neogloboquadrina pachyderma from a Gulf of Lions piston core indicate that abrupt cold spells associated with Atlantic Heinrich events affected the Mediterranean. N. pachyderma (l.c.) is typical of (sub) polar waters in the open ocean. The southern edge of its glacial North Atlantic bioprovince reached south Portugal. Only trace abundances of N. pachyderma (l.c.) are known from Quaternary Mediterranean sediments, suggesting that no significant "invasions" occured via the Strait of Gibraltar. The Gulf of Lions abundance peaks therefore seem to reflect area-specific thriving of a normally rare but indigenous taxon in the western Mediterranean through local favorable habitat development. The general planktonic foraminiferal record suggests that the basic hydrographic regime in the Gulf of Lions, with wintertime deep convective overturn, was relatively stable over the past 60 kyr. Under these conditions, high abundances of N. pachyderma (l.c.) would essentially imply temperature reductions of the order of 5°-8° relative to the present.

(Table T1) Kerogen and organic constituents in ODP Hole 183-1138A, Kerguelen Plateau

Mid-Cretaceous sediments recovered during Ocean Drilling Program Leg 183 (Cores 183-1138A-69R to 73R) on the central Kerguelen Plateau have been analyzed palynologically and paleobotanically to determine the age of the strata and to reconstruct vegetational development and paleoecology. The lower strata (Cores 183-1138A-71R to 73R), a dark, organic-rich silty claystone with many wood fragments and fern remains (sedimentary Unit VI), certainly of terrestrial origin, directly overlies the volcanic basement, which is dated as latest Albian (~95 to 103 Ma) to earliest Cenomanian. The age of the terrestrial strata can be determined by sporomorphs as late Albian to earliest Cenomanian as well. This shows that parts of the central Kerguelen Plateau must have been subaerial at least until the late Albian and were covered with a diverse high-latitude flora, probably dense conifer forest with various fern taxa in the undergrowth. Early angiosperms are also present. The vegetational character represented in Unit VI did not change significantly through time. However, varying percentages of several sporomorph groups seem to show recurring abundance variations, which might possibly be cyclic, caused by Milankovitch-type cyclic events. Cores 183-1138A-67R through 69R, of open marine origin, contain medium- to high-diversity dinocyst assemblages. Based on previous stratigraphic zonation schemes, the ages of these strata range within the Heterosphaeridium Superzone, from the Palaeohystrichophora infusorioides Zone to the Conosphaeridium striatoconus Zone, which correlates to the latest Cenomanian to Coniacian.

(Table 1) Stable carbon isotope ratios of methane and carbon dioxide from ODP Leg 169S holes

Sites 1033 and 1034 of ODP Leg 169S in Saanich Inlet have an unusual diagenetic system, that has the appearance of being depth reversed, i.e. a bacterial methane accumulation zone underlain by a sulphate reduction zone. During the late Pleistocene grey, undifferentiated, glacio-marine clays were deposited with low Corg contents (<0.4 wt.%), and interstitial fluids replete in SO4 (ca. 27 mM), devoid of CH4 and low in nutrients. This indicates oxic conditions are present, reflecting the open exchange of waters with Haro Strait during the Pleistocene before the Saanich Peninsula emerged. In the earliest Holocene (ca. 11,000 years BP) the inlet was formed, severely restricting water circulation, and leading to the presence of anoxic bottom waters. The sediments are laminated and show a dramatic rise to high Corg, Norg and Stot contents (up to 2.5, 0.4, 1.4 wt.%, respectively) over a period of ca. 1000 years. The nutrient concentrations are especially high (TA, NH4, PO4 up to 115 meq/l, 20 mM and 400 µM, respectively), SO4 is exhausted and CH4 is prolific. Stable carbon isotope ratio measurements of CH4 and co-existing CO2 indicate that methanogenesis is via carbonate reduction (delta13C-CH4 ca. -60 to - 70 per mil, delta13C-CO2 ca. +10 per mil). At the sulphate-methane interfaces, both at the near-surface and at 50 mbsf (Site 1033) and 80 mbsf (Site 1034) methane consumption by sulphate reducing bacteria is intensive.

(Table 1) Lipid biomarkers in surface sediments from the Gulf of Genoa

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, aeolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1 to 30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK'37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.

(Table 1) Rates of biological activity in deep-sea sediments

Global maps of sulfate and methane in marine sediments reveal two provinces of subsurface metabolic activity: a sulfate-rich open-ocean province, and an ocean-margin province where sulfate is limited to shallow sediments. Methane is produced in both regions but is abundant only in sulfate-depleted sediments. Metabolic activity is greatest in narrow zones of sulfate-reducing methane oxidation along ocean margins. The metabolic rates of subseafloor life are orders of magnitude lower than those of life on Earth's surface. Most microorganisms in subseafloor sediments are either inactive or adapted for extraordinarily low metabolic activity.

(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

(Table S1) Geochemistry for sediment core MD02-2515

A high-resolution, 55-kyr long record of chalcophile and redox-sensitive trace element accumulation (Ag, Cd, Re, Mo) from MD02-2515, western Guaymas Basin, is investigated in conjunction with patterns in stratigraphy and productivity. High opal concentrations (~58 wt. %), representing increased diatom production, coincide with laminated sediments, and dilute the concentrations of organic carbon (Corg) and metals. A similarity between opal and normalized Corg, Ag and Cd concentrations suggests delivery to the sediments by diatom export production, while patterns in normalized Re and Mo accumulation suggest a different emplacement mechanism. Although Mo enrichment in organic-rich, laminated sediments typically represents anoxic conditions at other locations, Mo (and Re) in Guaymas Basin is enriched in nonlaminated and bioturbated sediments that are representative of oxygenated conditions. Adsorption onto Fe- and/or Mn-oxyhydroxide surfaces during oxygenation inadequately explains both the Re and Mo enrichments. Thus, recently published mechanisms invoking direct Re and Mo removal from the water column and bioturbation-assisted irrigation of Re into the sediments are used to explain the counterintuitive observations in Guaymas Basin. The MD02-2515 stratigraphic and proxy records are also different from other records in the northeast Pacific in that there is little correspondence with Greenland Dansgaard-Oeschger interstadials. There is some correlation with Heinrich events, suggesting that ventilation of intermediate waters and/or reduced productivity may be important in controlling stratigraphy and trace element accumulation. The results question whether MD02-2515 records can be compared to northeast Pacific open-margin records, especially before 17 kyr BP.