Hydrogen and oxygen isotopes in ground lce of Bykovsky Peninsula, North Siberia

In wide areas of Northern Siberia, glaciers have been absent since the Late Pleistocene. Therefore, ground ice and especially ice wedges are used as archives for paleoclimatic studies. In the present study, carried out on the Bykovsky Peninsula, eastern Lena Delta, we were able to distinguish ice wedges of different genetic units by means of oxygen and hydrogen isotopes. The results obtained by this study on the Ice Complex, a peculiar periglacial phenomenon, allowed the reconstruction of the climate history with a subdivision of a period of very cold winters (60-55 ka), followed by a long stable period of cold winter temperatures (50-24 ka), Between 20 ka and I I ka, climate warming is indicated in stable isotope compositions, most probably after the Late Glacial Maximum. At that time, a change of the marine source of the precipitation from a more humid source to the present North Atlantic source region was assumed. For the Ice Complex, a continuous age-height relationship was established, indicating syngenetic vertical ice wedge growth and sediment accumulation rates of 0.7 m/ky. During the Holocene optimum, ice wedge growth was probably limited due to the extensive formation of lacustrine environments. Holocene ice wedges in thermokarst depressions (alases) and thermoerosional valleys (logs) were formed after climate deterioration from about 4.5 ka until the present. Winter temperatures were warmer at this time as compared to the cooler Pleistocene. Migration of bound water between ice wedges and segregated ice may have altered the isotopic composition of old ice wedges. The presence of ice wedges as diagnostic features for permafrost conditions since 60 ka, implies that a large glacier extending over the Laptev Sea shelf did not exist. For the remote non-glaciated areas of Northern Siberia, ice wedges were established as a powerful climate archive.

Isotope record and major element chemistry of intestitial waters of ODP Leg 104 sites

The variations in major elements and isotope composition (87Sr/86Sr, delta18O, deltaD) of interstitial waters in Leg 104 sediments is most probably caused by the alteration of volcanic matter. A reaction scheme where volcanic glass reacts with pore-water magnesium and potassium to form trioctahedral smectite, phillipsite, and chert is proposed. Model calculations demonstrate that the pore waters may evolve their negative 6180 signatures without recourse to unreasonably large amounts of volcanic detritus or external sources.

Carbon cycle change in the Eocene

The transition from the extreme global warmth of the early Eocene 'greenhouse' climate ~55 million years ago to the present glaciated state is one of the most prominent changes in Earth's climatic evolution. It is widely accepted that large ice sheets first appeared on Antarctica ~34 million years ago, coincident with decreasing atmospheric carbon dioxide concentrations and a deepening of the calcite compensation depth in the world's oceans, and that glaciation in the Northern Hemisphere began much later, between 10 and 6 million years ago. Here we present records of sediment and foraminiferal geochemistry covering the greenhouse-icehouse climate transition. We report evidence for synchronous deepening and subsequent oscillations in the calcite compensation depth in the tropical Pacific and South Atlantic oceans from ~42 million years ago, with a permanent deepening 34 million years ago. The most prominent variations in the calcite compensation depth coincide with changes in seawater oxygen isotope ratios of up to 1.5 per mil, suggesting a lowering of global sea level through significant storage of ice in both hemispheres by at least 100 to 125 metres. Variations in benthic carbon isotope ratios of up to ~1.4 per mil occurred at the same time, indicating large changes in carbon cycling. We suggest that the greenhouse-icehouse transition was closely coupled to the evolution of atmospheric carbon dioxide, and that negative carbon cycle feedbacks may have prevented the permanent establishment of large ice sheets earlier than 34 million years ago.

Strontium isotope geochemistry of ODP Leg 113 sites

The concentration of dissolved Sr and the distribution of 87Sr/86Sr isotope ratios in Leg 113 interstitial waters may be interpreted in terms of mixing of Sr from four different reservoirs: indigenous seawater, marine carbonate minerals, and basaltic and siliceous detrital material. The input to the pore water from these reservoirs is determined by the reactivity of the reservoir rather than its size. The presence of strontium derived from siliceous detrital material is unequivocally demonstrated in the pore waters of the hemipelagic deposits, and is also significant in the calcareous Maud Rise sediments due to the unusually low degree of carbonate recrystallization. Also, alteration of basic volcanic material is important at several sites.

Water chemistry and heat budget of the Churchill River estuary region

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April-May. In the Churchill Estuary, conditions varied abruptly throughout winter-spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (~6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter-spring transition, which implies sensitivity to climate change.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Stable oxygen isotope. Mg/Ca and Temperature record of Caribbean and Pacific sediments

The final phase of the closure of the Panamanian Gateway and the intensification of Northern Hemisphere Glaciation (NHG) both occurred during the Late Pliocene. Glacial-interglacial (G-IG) variations in sea level might, therefore, have had a significant impact on the remaining connections between the East Pacific and the Caribbean. Here, we present combined foraminiferal Mg/Ca and d18O measurements from Ocean Drilling Program (ODP) Site 1241 from the East Pacific and ODP Site 999 from the Caribbean. The studied time interval covers the first three major G-IG Marine Isotope Stages (MIS 95-100, ~2.5 Ma) after the intensification of NHG. Analyses were performed on the planktonic foraminifera Neogloboquadrina dutertrei and Globigerinoides sacculifer, representing water mass properties in the thermocline and the mixed-layer, respectively. Changes in sea water temperature, relative salinity, and water column stratification strongly suggest that the Panamanian Gateway temporarily closed during glacial MIS 98 and 100, as a result of changes in ice volume equivalent to a drop in sea level of 60-90 m. Reconstructed sea surface temperatures (SST) from G. sacculifer show a glacial decrease of 2.5°C at Site 1241, but increases of up to 3°C at Site 999 during glacial MIS 98 and 100 suggesting that the Panamanian Gateway closed during these glacial periods. The Mg/Ca-temperatures of N. dutertrei remain relatively stable in the East Pacific, but do show a 3°C warming in the Caribbean at the onset of these glacial periods suggesting that the closing of the gateway also changed the water column stratification. We infer that the glacial closure of the gateway allowed the Western Atlantic Warm Pool to extend into the southern Caribbean, increasing SST (G. sacculifer) and deepening the thermocline (N. dutertrei). Additionally, ice volume appears to have become large enough during MIS 100 to survive the relatively short lasting interglacial MIS 99 so that the gateway remained closed. Towards the end of MIS 98, during MIS 97 and into MIS 96 temperatures on both sides are mostly similar suggesting water masses exchanged again. Additionally, Caribbean variations in SST and d18Owater follow a precession-like cyclicity rather than the obliquity-controlled variations characteristic of the East-Pacific and many other tropical areas, suggesting that regional atmospheric processes related to the trade winds and the Intertropical Convergence Zone (ITCZ) had a dominant impact in the Caribbean.

Isotopic composition of diagenetic silica and associated pore waters of Japan Sea sediments

Over a broad region of the eastern Japan Sea, Neogene opaline diatomaceous sediments alter with depth to hard porcellanites and cherts composed of opal-CT and quartz. We examined the oxygen isotopic compositions of these diagenetic silica minerals at four widely spaced sites occupied during ODP Leg 127 in order to investigate the thermal history of the region. Formation temperatures computed from these isotopic data range from 22° to 68°C for opal-CT and from 44° to 92°C for diagenetic quartz, quite similar to temperature ranges estimated from the extrapolated modern gradients, 36°-43°C and 49°-64°C, respectively. At each site the isotopic temperature values cluster near the extrapolated ambient sediment temperatures. As a first approximation, the similarities suggest that the positions of the silica transformations in the basin are controlled by the present thermal regime. In detail, isotopic and ambient temperatures differ. If these differences are real, then they reflect variations in the thermal histories at these sites. At Sites 794 and 797 in the Yamato Basin, isotopic temperatures and gradients computed from these data are lower than or comparable to ambient temperatures and gradients. We suggest that the silica zones have roughly equilibrated with the modern gradients at these localities. At Site 795 in the Japan Basin, isotopic temperatures are also lower than ambient sediment temperatures at comparable depths, but the gradient computed from the isotopic temperatures is higher than the present measured gradient. For both scenarios to hold, the silica zones must have formed under initially high gradients during the early post-rift period at this locality. These zones were then rapidly buried and have yet to equilibrate with the modern lower gradient. At Site 796 on Okushiri Ridge, isotopic temperatures exceed present temperatures as expected for an area of recent uplift. The gradient computed from our isotopic data and the thickness of the opal-CT zone indicate a higher gradient than at present at this site, apparently reflecting higher heat fluxes during the early post-rift period or recent frictional heating from nearby reverse fault activity.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Stable isotope record of planktic foraminifera sampled by plankton haul and in surface sediments off North-West Africa

Foraminifera shells from modern sediments document the hydrography of the coastal upwelling region off Northwest-Africa (12-35° N) through the stable isotopic composition of their shells. Oxygen isotopes in planktonic foraminifers reflect sea surface temperatures (SST) during the main growing season of the differnt species: Globigerinoides ruber (pink and white) and G. sacculifer delineate the temperatures of the summer, Globorotalia inflata and Pulleniatina obliquiloculata those of the winter. Oxygen isotopes on Globigerina bulloides document temperature ranges of the upwelling seasons. d18O values in planktonic foraminifera from plankton hauls resemble those from the surface sediment samples, if the time of the plankton collection is identical with that of the main growing season of the species. The combined isotopic record of G. ruber (white) and G. inflata clearly reveals the latitudinal variations of the annual mean SST. The deviation of the d18O values from both species from their common mean is a scale for the seasonality, i.e. the maximum temperature range within one year. Thus in the summer upwelling region (north of 25° N) seasonality is relatively low, while it becomes high in the winter upwelling region south of 20° N. Furthermore, the winter upwelling region is characterized by relatively high d18O values - indicating low temperatures - in G. bulloides, the region of summer upwelling by relatively low d180 values compared with the constructed annual mean SST. Generally, carbon isotopes from the plankton hauls coincide with those from sediment surface samples. The enrichment of 13C isotopes in foraminifers from areas with high primary production can be caused by the removal of 12C from the total dissolved inorganic carbon during phytoplankton blooms. It is found that carbon isotopes from plankton hauls off Northwest-Africa are relatively enriched in 13C compared with samples from the western Atlantic Ocean. Also shells of G. ruber (pink and white) from upwelling regions are enriched in the heavier isotope compared with regions without upwelling. In the sediment, the enrichement of 13C due to high primary production can only be seen in G. bulloides from the high fertile upwelling region south of 20° N. North of this latitude values are relatively low. An enrichment of 12C is observed in shells of G. ruber (pink), G. inflata and P. obliquiloculata from summer-winter- and perennial upwelling regions respectively. Northern water masses can be distinguished from their southern counterparts by relatively high oxygen and carbon values in the "living" (=stained) benthic foraminifera Uvigerina sp. and Hoeglundina elegans. A tongue of the Mediterranean Outflow water can be identified far to the south (20° N) by 13C-enriched shells of these benthic foraminifera. A zone of erosion (15-25° N, 300-600 m) with a subrecent sediment surface can be mapped with the help of oxygen isotopes in "dead" benthic specimens. Comparison of d18O values in aragonitic and calcitic benthic foraminifers does not show a differential influence of temperature on the isotopic composition in the carbonate. However, carbon isotopes reflect slightly differences under the influence of temperature.

Geochemistry of ODP Site 202-1233 and river sediments

Bulk sediment chemistry from three Chilean continental margin Ocean Drilling Program sites constrains regional continental erosion over the past 30,000 years. Sediments from thirteen rivers that drain the (mostly igneous) Andes and the (mostly metamorphic) Coast Range, along with existing rock chemistry datasets, define terrestrial provenance for the continental margin sediments. Andean river sediments have high Mg/Al relative to Coast-Range river sediments. Near 36°S, marine sediments have high-Mg/Al (i.e. more Andean) sources during the last glacial period, and lower-Mg/Al (less Andean) sources during the Holocene. Near 41°S a Ti-rich source, likely from coast-range igneous intrusions, is prevalent during Holocene time, whereas high-Mg/Al Andean sources are more prevalent during the last glacial period. We infer that there is a dominant ice-sheet control of sediment sources. At 36°S, Andean-sourced sediment decreased as Andean mountain glaciers retreated after ~17.6 ka, coincident with local oceanic warming and southward retreat of the Patagonian Forest and, by inference, westerly winds. At 41°S Andean sediment dominance peaks and then rapidly declines at ~19 ka, coincident with local oceanic warming and the earliest deglacial sea-level rise. We hypothesize that this decreased flux of Andean material in the south is related to rapid retreat of the marine-based portion of the Patagonian Ice Sheet in response to global sea-level rise, as the resulting flooding of the southern portion of the Central Valley created a sink for Andean sediments in this region. Reversal of the decreasing deglacial Mg/Al trend at 41°S from 14.5 to 13.0 ka is consistent with a brief re-advance of the Patagonian ice sheet coincident with the Antarctic Cold Reversal.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Density and stable oxygen isotope profiles of four snow pits from Berkner Island, Filchner-Ronne Ice Shelf, Antarctica

The ice cap on Berkner Island is grounded on bedrock within the Filchner-Ronne Ice Shelf and is, therefore, expected to be a well-suited place to retrieve long-term ice-core records reflecting the environmental situation of the Weddell Sea region. Shallow firn cores were drilled to 11 m at the two main summits of Berkner Island and analysed in high depth resolution for electrical d.c. conductivity (ECM), stable isotopes, chloride, sulphate, nitrate and methane-sulphonate (MSA). From the annual layering of dD and non-sea-salt (nss) sulphate, a mean annual snow accumulation of 26.6 cm water at the north dome and 17.4 cm water at the south dome are obtained. As a result of ineffective wind scouring indicated by a relatively low near-surface snow density, regular annual cycles are found for all species at least in the upper 4-5 m. Post depositional changes are responsible for a substantial decrease of the seasonal dD and nitrate amplitude as well as for considerable migration of the MSA signal operating below a depth of 3-4 m. The mean chemical and isotopic firn properties at the south dome correspond to the situation on the Filchner-Ronne Ice shelf at a comparable distance to the coast, whereas the north dome is found to be more influenced by maritime air masses. Persistent high sea-salt levels in winter snow at Berkner Island heavily obscure the determination of nss sulphate probably due to sulphate fractionation in the Antartic sea-salt aerosols. Estimated time-scales predict ages at 400 m depth to be ca. 2000 years for the north and ca. 3000 years for the south dome. Pleistocene ice is expected in the bottom 200 and 300 m, respectively.

AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

Physical and chemical investigations on ice cores from the Filchner-Ronne Ice Shelf

The accumulation and distribution of the 2H content of near-surface layers in the eastern part of the Ronne Ice Shelf were determined from 16 firn cores drilled to about 10 m depth during the Filchner IIIa and IV campaigns in 1990 and 1992, respectively. The cores were dated stratigraphically by seasonal d2H variations in the firn. In addition, 3H and high-resolution chemical profiles were used to assist in dating. Both the accumulation rate and the stable-isotope content decrease with increasing distance from the ice edge: the d2H values range from about -195 per mil at the ice edge to -250 per mil at BAS sites 5 and 6, south of Henry Ice Rise, and the accumulation rates from about 210 to 90 kg/m**2/a. The d2H values of the near-surface firn and the 10 m firn temperatures (Theta) at individual sites are very well correlated: ddelta2H/dTheta=(10.3±0.6)per mil /K; r = 0.97. The d2H profiles of the two ice cores B13 and B15 drilled in 1990 and 1992 to 215 and 320 m depth, respectively, reflect the gradual depletion in 2H in the firn upstream of the drill sites. Comparison with tlie surface data indicates that the ice above 142 m in core B15 and above 137 m in core B13 was deposited on the ice shelf, whereas the deeper ice, down to 152.8 m depth, most probably originated from the margin of the Antarctic ice sheet.