(Table 1) Carbon and isotopic composition of organic carbon in sediments from DSDP Leg 56 Holes

We have analyzed inorganic and organic carbons and determined the isotopic composition of both sedimentary organic carbon and inorganic carbon in carbonates contained in sediments recovered from Holes 434, 434A, 434B, 435, and 435A in the landward slope of Japan and from Hole 436 in the oceanic slope of the Japan Trench. Both inorganic and organic carbons were assayed at the P. P. Shirshov Institute of Oceanology, in the same sample, using the Knopp technique and measuring evolved CO2 gravimetrically. Each sample was analyzed twice in parallel. Measurements were of a ±0.05 per cent accuracy and a probability level of 0.95. Carbon isotopic analysis was carried out on a MI-1305 mass spectrometer at the I. M. Gubkin Institute of Petrochemical and Gas Industry and the results presented as dC13 values related to the PDB standard. The procedure for preparing samples for organic carbon isotopic analysis involved (1) drying damp sediments at 60°C; (2) treating samples, while heating, with 10 N HCl to remove carbonate carbon; and (3) evaporating surplus HCl at 60°C. The organic substance was turned to CO2 by oxidizing it in an oxygen atmosphere. To prepare samples for inorganic carbon isotopic analysis we decomposed the carbonates with orthophosphoric acid and refined the gas evolved. The dC13 measurements, including a full cycle of sample preparation, were of a ±0.5 per cent accuracy and a probability level of 0.95.

Pliocene-Pleistocene stack of globally distributed benthic stable oxygen isotope records

We present a 5.3-Myr stack (the ''LR04'' stack) of benthic d18O records from 57 globally distributed sites aligned by an automated graphic correlation algorithm. This is the first benthic delta18O stack composed of more than three records to extend beyond 850 ka, and we use its improved signal quality to identify 24 new marine isotope stages in the early Pliocene. We also present a new LR04 age model for the Pliocene-Pleistocene derived from tuning the delta18O stack to a simple ice model based on 21 June insolation at 65 N. Stacked sedimentation rates provide additional age model constraints to prevent overtuning. Despite a conservative tuning strategy, the LR04 benthic stack exhibits significant coherency with insolation in the obliquity band throughout the entire 5.3 Myr and in the precession band for more than half of the record. The LR04 stack contains significantly more variance in benthic delta18O than previously published stacks of the late Pleistocene as the result of higher resolution records, a better alignment technique, and a greater percentage of records from the Atlantic. Finally, the relative phases of the stack's 41- and 23-kyr components suggest that the precession component of delta18O from 2.7-1.6 Ma is primarily a deep-water temperature signal and that the phase of d18O precession response changed suddenly at 1.6 Ma.

Geochemistry, isotopic ratios and aldehyde concentrations of frost flowers, snow and ice near Barrow, Alaska

Frost flowers, intricate featherlike crystals that grow on refreezing sea ice leads, have been implicated in lower atmospheric chemical reactions. Few studies have presented chemical composition information for frost flowers over time and many of the chemical species commonly associated with Polar tropospheric reactions have never been reported for frost flowers. We undertook this study on the sea ice north of Barrow, Alaska to quantify the major ion, stable oxygen and hydrogen isotope, alkalinity, light absorbance by soluble species, organochlorine, and aldehyde composition of seawater, brine, and frost flowers. For many of these chemical species we present the first measurements from brine or frost flowers. Results show that major ion and alkalinity concentrations, stable isotope values, and major chromophore (NO3- and H2O2) concentrations are controlled by fractionation from seawater and brine. The presence of these chemical species in present and future sea ice scenarios is somewhat predictable. However, aldehydes, organochlorine compounds, light absorbing species, and mercury (part 2 of this research and Sherman et al. (2012, doi:10.1029/2011JD016186)) are deposited to frost flowers through less predictable processes that probably involve the atmosphere as a source. The present and future concentrations of these constituents in frost flowers may not be easily incorporated into future sea ice or lower atmospheric chemistry scenarios. Thinning of Arctic sea ice will likely present more open sea ice leads where young ice, brine, and frost flowers form. How these changing ice conditions will affect the interactions between ice, brine, frost flowers and the lower atmosphere is unknown.

(Table 2) Stable carbon and oxygen isotope record of benthic foraminifera of eastern Mediterranean Sea sediment cores

The paleoproductivity, paleo-oxygenation, and paleohydrographic configuration of the southeastern Mediterranean during the late Holocene was reconstructed on the basis of the isotopic composition of the epibenthic Heterolepa floridana, shallow-endobenthic Uvigerina mediterranea, and the deeper endobenthic Bulimina inflata from two high-resolution cores GA-112 (470 m) and GA-110 (670 m). The Delta d13C between H. floridana and U. mediterranea reveals four intervals of enhanced productivity, from 3.3-2.6, 2.3-1.9, 1.5-1.1, and 0.8-0.4 kyr BP, coinciding with increased nutrient supply by the Nile River. The entire basin was well aerated, with oxygen consumption varying between 1.0 and 3.5 mL O2/L. Oxygen consumption increases toward present day, probably because of higher accumulation of total organic carbon at 1.7 kyr BP, coinciding with the appearance of the mesotropic benthic species. The hydrographic configuration of the basin has changed during the course of the last 3.75 kyr. The Levantine Intermediate Water (LIW) deepens below 470 m between 3.3 and 2.0 kyr, and especially between 2.5 and 2.0 kyr. During the last 1.5 kyr, the LIW becomes shallower than 470 m, similar to the present day. The change in the hydrographic configuration reflects changes in evaporation/precipitation ratio and in temperature.

O, C and Sr isotopic data for plankton and benthic foraminifera from DSDP Legs 26, 32, 36, and 71 sediments

A detailed d18O and d13C stratigraphy has been generated from analysis of well-preserved Albian - Early Maastrichtian foraminifera from Deep Sea Drilling Project (DSDP) Sites 511 and 327 (Falkland Plateau; ~58°S - 62°S paleolatitude) in the southern South Atlantic, and Cenomanian and Coniacian - Santonian foraminifera from DSDP Site 258 (Naturaliste Plateau; ~58°S paleolatitude) in the southern Indian Ocean. These results, when combined with previously published Maastrichtian stable isotope data from Ocean Drilling Program (ODP) Site 690 (Weddell Sea, ~65°S paleolatitude), provide new insight into the climatic and oceanographic history of the southern high latitudes during Middle-Late Cretaceous time. The planktonic foraminifer d18O curves reveal a gradual warming of surface waters from the Albian through the Cenomanian followed by extremely warm surface waters from the Turonian through the early Campanian. Long-term cooling of surface waters began in the late early Campanian and continued through the end of the Maastrichtian. The benthic foraminifer d18O record generally parallels changes in the oxygen isotopic curves defined by shallow-dwelling planktonic foraminifera. The vertical oxygen and carbon isotopic gradients were relatively low during the Albian - Cenomanian, high from the Turonian - Early Campanian, and then low during the late Campanian and Maastrichtian.

Radiocarbon ages, dose rates, water isotopic composition and hydrochemistry of samples from Komakuk Beach and Herschel Island

Terrestrial permafrost archives along the Yukon Coastal Plain (northwest Canada) have recorded landscape development and environmental change since the Late Wisconsinan at the interface of unglaciated Beringia (i.e. Komakuk Beach) and the northwestern limit of the Laurentide Ice Sheet (i.e. Herschel Island). The objective of this paper is to compare the late glacial and Holocene landscape development on both sides of the former ice margin based on permafrost sequences and ground ice. Analyses at these sites involved a multi-proxy approach including: sedimentology, cryostratigraphy, palaeoecology of ostracods, stable water isotopes in ground ice, hydrochemistry, and AMS radiocarbon and infrared stimulated luminescence (IRSL) dating. AMS and IRSL age determinations yielded full glacial ages at Komakuk Beach that is the northeastern limit of ice-free Beringia. Herschel Island to the east marks the Late Wisconsinan limit of the northwest Laurentide Ice Sheet and is composed of ice-thrust sediments containing plant detritus as young as 16.2 cal ka BP that might provide a maximum age on ice arrival. Late Wisconsinan ice wedges with sediment-rich fillings on Herschel Island are depleted in heavy oxygen isotopes (mean d18O of -29.1 per mil); this, together with low d-excess values, indicates colder-than-modern winter temperatures and probably reduced snow depths. Grain-size distribution and fossil ostracod assemblages indicate that deglaciation of the Herschel Island ice-thrust moraine was accompanied by alluvial, proluvial, and eolian sedimentation on the adjacent unglaciated Yukon Coastal Plain until ~11 cal ka BP during a period of low glacio-eustatic sea level. The late glacial-Holocene transition was marked by higher-than-modern summer temperatures leading to permafrost degradation that began no later than 11.2 cal ka BP and caused a regional thaw unconformity. Cryostructures and ice wedges were truncated while organic matter was incorporated and soluble ions were leached in the thaw zone. Thermokarst activity led to the formation of ice-wedge casts and deposition of thermokarst lake sediments. These were subsequently covered by rapidly accumulating peat during the early Holocene Thermal Maximum. A rising permafrost table, reduced peat accumulation, and extensive ice-wedge growth resulted from climate cooling starting in the middle Holocene until the late 20th century. The reconstruction of palaeolandscape dynamics on the Yukon Coastal Plain and the eastern Beringian edge contributes to unraveling the linkages between ice sheet, ocean, and permafrost that have existed since the Late Wisconsinan.

Stable carbon and oxygen isotope composition of benthic foraminifera

Seventeen surface sediment samples from the North Atlantic Ocean off NE-Greenland between 76° and 81°N, and nine samples from the South Atlantic Ocean close to Bouvet Island between 48° and 55°S were taken with the aid of a Multiple Corer and investigated for their live (Rose Bengal stained) benthic foraminiferal content within the upper 15 cm of sediment. Preferentially endobenthic Melonis barleeanum, Melonis zaandami, and Bulimina aculeata as well as preferentially epibenthic Lobatula lobatula were counted from 1-cm-thick sediment slices each and analyzed for stable carbon and oxygen isotopic compositions of their calcareous tests. Live and dead specimens were counted and measured separately. The carbon isotopic composition of the foraminifera was compared to that of the dissolved inorganic carbon (DIC) of simultaneously sampled bottom water. During a period of one month, one station off NE-Greenland was replicately sampled once every week and samples were processed as above. Live specimens of Lobatula lobatula are confined to the uppermost two centimeters of sediment. Live specimens of Melonis spp. are found down to 8 cm within the sediment but with a distinct sub-surface maximum between 2 and 5 cm. The down-core distribution of live Bulimina aculeata shows a distinct surface maximum in the top centimeter and constant but low numbers down to 11-cm subbottom depth. The average stable carbon isotopic composition (d13C versus per mil PDB) of live Lobatula lobatula off NE-Greenland is by 0.4±0.1 per mil higher than the d13CDIC of the ambient bottom water at the time of sampling. There is evidence that this species calcify before the ice-free season, when bottom water d13CDIC is supposed to be higher. This would reconfirm the one-to-one relationship between d13C of ambient water DIC and cibicids, widely used by paleoceanographers. Live Melonis barleeanum show a negative offset from bottom water DIC of -1.7±0.6 per mil in the uppermost sediment and of -2.2±0.5 per mil in 3-4-cm subbottom depth. All d13C values of live Melonis spp. decrease within the upper four centimeters, regardless of the time of sampling and site investigated. The offset of live Bulimina aculeata from bottom water d13CDIC values of 8 stations rather constantly amounts to -0.6±0.1 per mil, no matter what subbottom depth the specimens are from. At one station however, where is strong indication of elevated organic carbon flux, the negative offset averaged over all sub-bottom depths increases to -1.5±0.2 per mil. Buliminids actively move within the sediment and by this either record an average isotope signal of the pore water or the signal of one specific calcification depth. The recorded signal, however, depends on the organic carbon flux and reflects general but site-specific pore water d13CDIC values. If compared with epibenthic d13C values from the same site, not influenced by pore water and related phytodetritus layer effects, Buliminad13C values bear some potential as a paleoproductivity proxy. Specimens of Melonis spp. seem to prefer a more static way of life and calcify at different but individually fix depths within the sediment. Although live specimens thus record a stratified pore water d13C signal, there is no means yet to correct for bioturbational and early diagenetic effects in fossil faunas.

(Table 2) Oxygen and carbon isotope composition of planktonic foraminiferal species from DSDP Holes 93-603B and 93-604, and one benthic species from Hole 93-604

Holes 603C and 604 of DSDP Leg 93 were drilled on the western Atlantic continental rise at water depths of 4633 m and 2364 m, respectively. In Hole 603C, a nearly continuous, undisturbed, and complete section of Pliocene and lower Pleistocene sediments was recovered by hydraulic piston coring; in Hole 604, a section of uppermost Miocene to Pleistocene sediments was incompletely recovered by rotary coring. In order to reconstruct the Pliocene and Pleistocene history of isotopic variations, 139 oxygen and carbon isotope values were determined for planktonic and monospecific benthic foraminifer samples from these holes. Large parts of the Pleistocene history could not, however, be documented because sample intervals were large and sediments at Site 604 were redeposited. Time correlation is based on magnetostratigraphic (Hole 603C) and micropaleontologic (Hole 603C, Site 604) interpretation. Stable isotope analyses were carried out on the planktonic foraminiferal species Globigerinoides ruber, G. obliquus, and Globorotalia inflata from Hole 603C (48 analyses) and from Site 604 (48 analyses); at Site 604, the benthic foraminifer Uvigerina peregrina (43 analyses) was also studied through the section. Age calibration for Hole 603C is based on the magnetostratigraphy of Canninga et al. (1987; doi:10.2973/dsdp.proc.93.130.1987), which uses the time scale of Lowrie and Alvarez (1981).