(Tabls S1) Bulk geochemistry for sediment samples collected from the Cenomanian-Turonian boundary section at Pont d'Issole

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The d13Ccarb, d13Corg, and d18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). Delta13C (offset between d13Ccarb and d13Corg) is shown to be a good pCO2 proxy that is consistent with pCO2 records obtained using biomarker d13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk d18O records show sea surface temperature (SST) changes that closely follow the Delta13C pCO2 proxy and confirm TEX86 results from deep ocean sites. Rising pCO2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO2 minimum (~25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4°C of cooling in ~40 kyr. Renewed increases in pCO2, SST, and d13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO2 flux overrode further drawdown effects. Maximum pCO2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand.

Isotopic composition of ground ice, ebullition gases and thermokarst lake water, North America

Thermokarst lakes are thought to have been an important source of methane (CH4) during the last deglaciation when atmospheric CH4 concentrations increased rapidly. Here we demonstrate that meltwater from permafrost ice serves as an H source to CH4 production in thermokarst lakes, allowing for region-specific reconstructions of dD-CH4 emissions from Siberian and North American lakes. dD CH4 reflects regionally varying dD values of precipitation incorporated into ground ice at the time of its formation. Late Pleistocene-aged permafrost ground ice was the dominant H source to CH4 production in primary thermokarst lakes, whereas Holocene-aged permafrost ground ice contributed H to CH4 production in later generation lakes. We found that Alaskan thermokarst lake dD-CH4 was higher (-334 ± 17 per mil) than Siberian lake dD-CH4 (-381 ± 18 per mil). Weighted mean dD CH4 values for Beringian lakes ranged from -385 per mil to -382 per mil over the deglacial period. Bottom-up estimates suggest that Beringian thermokarst lakes contributed 15 ± 4 Tg CH4 /yr to the atmosphere during the Younger Dryas and 25 ± 5 Tg CH4 /yr during the Preboreal period. These estimates are supported by independent, top-down isotope mass balance calculations based on ice core dD-CH4 and d13C-CH4 records. Both approaches suggest that thermokarst lakes and boreal wetlands together were important sources of deglacial CH4.

Benthic foraminifera extinctions in the Cenozoic record

In the late Pliocene-middle Pleistocene a group of 95 species of elongate, cylindrical, deep-sea (lower bathyal-abyssal) benthic foraminifera became extinct. This Extinction Group (Ext. Gp), belonging to three families (all the Stilostomellidae and Pleurostomellidae, some of the Nodosariidae), was a major component (20-70%) of deep-sea foraminiferal assemblages in the middle Cenozoic and subsequently declined in abundance and species richness before finally disappearing almost completely during the mid-Pleistocene Climatic Transition (MPT). So what caused these declines and extinction? In this study 127 Ext. Gp species are identified from eight Cenozoic bathyal and abyssal sequences in the North Atlantic and equatorial Pacific Oceans. Most species are long-ranging with 80% originating in the Eocene or earlier. The greatest abundance and diversity of the Ext. Gp was in the warm oceanic conditions of the middle Eocene-early Oligocene. The group was subjected to significant changes in the composition of the faunal dominants and slightly enhanced species turnover during and soon after the rapid Eocene-Oligocene cooling event. Declines in the relative abundance and flux of the Ext. Gp, together with enhanced species loss, occurred during middle-late Miocene cooling, particularly at abyssal sites. The overall number of Ext. Gp species present began declining earlier at mid abyssal depths (in middle Miocene) than at upper abyssal (in late Pliocene-early Pleistocene) and then lower bathyal depths (in MPT). By far the most significant Ext. Gp declines in abundance and species loss occurred during the more severe glacial stages of the late Pliocene-middle Pleistocene. Clearly, the decline and extinction of this group of deep-sea foraminifera was related to the function of their specialized apertures and the stepwise cooling of global climate and deep water. We infer that the apertural modifications may be related to the method of food collection or processing, and that the extinctions may have resulted from the decline or loss of their specific phytoplankton or prokaryote food source, that was more directly impacted than the foraminifera by the cooling temperatures.

Isotopic composition of modern ice wedges and winter precipitation in the Laptev Sea region (Table 2)

The first step for the application of stable isotope analyses of ice wedges for the correct paleoclimatic reconstruction supposes the study of the isotopic composition of modern ice wedges and their relationship with the isotopic composition of modern precipitation. The purpose of this research is to present, to analyze and to discuss new data on isotopic composition (d18O, dD, 3H) of modern ice wedges obtained in the Laptev Sea region in 1998-99. Investigations were carried out at two sites: on Bykovsky Peninsula in 1998 and on Bol'shoy Lyakhovsky Island in 1999 and were based on the combined application of both tritium CH) and stable isotope (d18O, dD) analyses. Tritium analyses of the atmospheric precipitation collected during two field seasons show seasonal variations: high tritium concentration in snow (to a maximum of 207 TU) and low values of tritium concentration (<20 TU) in rain. High tritium concentrations are also observed in the surface water, in suprapermafrost ground waters, and in the upper part of permafrost. High tritium concentrations range between 30-40 TU and 750 TU in the studied modern ice wedges (active ice wedges), which let us believe that they are of modern growth. Such high tritium concentrations in ice wedges can not be associated with old thermonuclear tritium because of the radioactive decay. High tritium concentrations found in the snow cover in 1998/99, in the active layer and in the upper part of permafrost give evidence of modern (probably the last decade) technogenic tritium arrival from the atmosphere on to the Earth surface in the region. The comparison of the isotopic composition (d18O, dD and d-excess) of active ice wedges and modern winter precipitation in both sites shows: 1) the isotopic composition of snow correlates linearly with a slope close to 8.0 and parallel to the GMWL at both sites; 2) the mean isotopic composition of active ice wedges on Bykovsky Peninsula is in good agreement with the mean isotopic composition of modern snow; 3) the isotopic composition of active ice wedges and snow on Bol'shoy Lyakhovsky Island are considerably different. There are low values of d-excess in all studied active ice wedges (mean value is about 4.8 per mil), while in snow, the mean value of d-excess is about 9.5 per mil. Possible reasons for this gap are the following: 1) the modification of the isotopic composition in snow during the spring period; 2) changes in the isotopic composition of ice wedges due to the process of ice sublimation in open frost cracks during the cold period; 3) mixing of snowmelt water with different types of surface water during the spring period; 4) different moisture source regions.

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.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

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.