Chemical composition of waters, suspended matter, bottom sediments, and benthic organisms along a section from the Ob River estuary (Obskaya Guba) to the central Kara Sea

Biogeochemical behavior of a group of heavy metals and metalloids in water (including their dissolved and suspended particulate forms), bottom sediments, and zoobenthos was studied in the Ob River estuary (Obskaya Guba) - Kara Sea section on the basis of data obtained during Cruise 54 of R/V Akademik Mstislav Keldysh in September-October 2007. Changes in ratios of dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and As were shown, as well as growth of adsorbed fractions of the elements in near-bottom suspended matter under mixing of riverine and marine waters. Features of chemical element accumulation in typical benthic organisms of the Obskaya Guba and the Kara Sea were revealed, and their concentrating factors were calculated based on specific conditions of the environment. It was shown that shells of bivalves possessing higher biomass compared to other groups of organisms in the Obskaya Guba play an important role in deposition of heavy metals. In the Obskaya Guba mollusks accumulate Cd and Pb at the background level, whereas Cu and Zn contents appear to be higher than the background level.

Benthic foraminifers, isotopes and varimax factors at DSDP Holes 72-517 and 72-518

Pliocene changes in the vertical water mass structure of the western South Atlantic are inferred from changes in benthic foraminiferal assemblages and stable isotopes from DSDP Holes 516A, 517, and 518. Factor analysis of 34 samples from Site 518 reveals three distinct benthic foraminiferal assemblages that have been associated with specific subsurface water masses in the modern ocean. These include a Nuttalides umbonifera assemblage (Factor 1) associated with Antarctic Bottom Water (AABW), a Globocassidulina subglobosa-Uvigerina peregrina assemblage (Factor 2) associated with Circumpolar Deep Water (CPDW), and an Oridorsalis umbonatus-Epistominella exigua assemblage associated with North Atlantic Deep Water (NADW). Bathymetric gradients in d13C between Holes 516A (1313 m), 517 (2963 m), and 518 (3944 m) are calculated whenever possible to monitor the degree of similarity and/or difference in the apparent oxygen utilization (AOU) of water masses located at these depths during the Pliocene. Changes in bathymetric d13C gradients coupled with benthic foraminiferal assemblages record fundamental changes in the vertical water mass structure of the Vema Channel during the Pliocene from 4.1 to 2.7 Ma. At Site 518, the interval from 4.1 to 3.6 Ma is dominated by the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages. The d13C gradient between Holes 518 (3944 m) and 516A (1313 m) undergoes rapid oscillations during this interval though no permanent increase in the gradient is observed. However, d13C values at Site 518 are clearly lighter during this interval. These conditions may be related to increased bottom water activity associated with the re-establishment of the West Antarctic Ice Sheet in the late Gilbert Chron (-4.2 to 3.6 Ma) (Osborn et al., 1982). The interval from 3.6 to 3.2 Ma is marked by a dominance of the G. subglobosa-U. peregrina (Factor 2) assemblage and lack of a strong d13C gradient between Holes 518 (3944 m) and 516A (1313 m). We suggest that shallow circumpolar waters expanded to depths of a least 3944 m (Site 518) during this time. The most profound faunal and isotopic change occurs at 3.2 Ma, and is marked by dominance of the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages, a 1.1 per mil enrichment in d18O, and a large negative increase in the d13C gradient between Holes 518 and 516A. These changes at Site 518 record the vertical displacement of circumpolar waters by AABW and NADW. This change in vertical water mass structure at 3.2 Ma was probably related to a global cooling event and/or final closure of the Central American seaway. A comparison of the present-day d13C structure of the Vema Channel with a reconstruction between 3.2 and 2.7 Ma indicates that circulation patterns during this late Pliocene interval were similar to those of the modern western South Atlantic.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

Planktic and benthic foraminifreral isotope data for ODP Site 207-1258

The mid-Cretaceous is widely considered the archetypal ice-free greenhouse interval in Earth history, with a thermal maximum around Cenomanian-Turonian boundary time (ca. 90 Ma). However, contemporaneous glaciations have been hypothesized based on sequence stratigraphic evidence for rapid sea-level oscillation and oxygen isotope excursions in records generated from carbonates of questionable preservation and/or of low resolution. We present new oxygen isotope records for the mid-Cenomanian Demerara Rise that are of much higher resolution than previously available, taken from both planktic and benthic foraminifers, and utilizing only extremely well preserved glassy foraminifers. Our records show no evidence of glaciation, calling into question the hypothesized ice sheets and rendering the origin of inferred rapid sea-level oscillations enigmatic. Simple mass-balance calculations demonstrate that this Cretaceous sea-level paradox is unlikely to be explained by hidden ice sheets existing below the limit of d18O detection.

Mg/Ca-temperature proxy in benthic foraminifera from the Florida Strait

Over the past decade, the ratio of Mg to Ca in foraminiferal tests has emerged as a valuable paleotemperature proxy. However, large uncertainties remain in the relationships between benthic foraminiferal Mg/Ca and temperature. Mg/Ca was measured in benthic foraminifera from 31 high-quality multicore tops collected in the Florida Straits, spanning a temperature range of 5.8° to 18.6°C. New calibrations are presented for Uvigerina peregrina, Planulina ariminensis, Planulina foveolata, and Hoeglundina elegans. The Mg/Ca values and temperature sensitivities vary among species, but all species exhibit a positive correlation that decreases in slope at higher temperatures. The decrease in the sensitivity of Mg/Ca to temperature may potentially be explained by Mg/Ca suppression at high carbonate ion concentrations. It is suggested that a carbonate ion influence on Mg/Ca may be adjusted for by dividing Mg/Ca by Li/Ca. The Mg/Li ratio displays stronger correlations to temperature, with up to 90% of variance explained, than Mg/Ca alone. These new calibrations are tested on several Last Glacial Maximum (LGM) samples from the Florida Straits. LGM temperatures reconstructed from Mg/Ca and Mg/Li are generally more scattered than core top measurements and may be contaminated by high-Mg overgrowths. The potential for Mg/Ca and Mg/Li as temperature proxies warrants further testing.

Cenomanian benthic foraminifera of Demerara Rise

This study is based on Cenomanian sediments of Ocean Drilling Program (ODP) Sites 1258 and 1260 from Demerara Rise (Leg 207, western tropical Atlantic, off Suriname, ~1000 and ~500 m paleo-water depth, respectively). Studied sediments consist of laminated black shales with TOC values between 3 and 18% and include the Mid Cenomanian Event (MCE), a positive carbon isotope excursion predating the well-known Oceanic Anoxic Event 2 (OAE 2). Benthic foraminiferal assemblages of the continuously eutrophic environment at Demerara Rise are characterized by low diversities (<= 9 species per sample) and large fluctuations in abundances, indicating oxygen depletion and varying organic matter fluxes. Dominant species at both sites are Bolivina anambra, Gabonita levis, Gavelinella dakotensis, Neobulimina albertensis, Praebulimina prolixa, and Tappanina cf. laciniosa. Benthic foraminiferal assemblages across the MCE show a threefold pattern: (1) stable ecological conditions below the MCE interval indicated by relatively high oxygenation and fluctuating organic matter flux, (2) decreasing oxygenation and/or higher organic matter flux during the MCE with decreasing benthic foraminiferal numbers and diversities (Site 1258) and a dominance of opportunistic species (Site 1260), and (3) anoxic to slightly dysoxic bottom-water conditions above the MCE as indicated by very low diversities and abundances or even the absence of benthic foraminifera. Slightly dysoxic conditions prevailed until OAE 2 at Demerara Rise. A comparison with other Atlantic Ocean and Tethyan sections indicates that the MCE reflects a paleoceanographic turning point towards lower bottom-water oxygenation, at least in the proto-North Atlantic Ocean and in the Tethyan and Boreal Realms. This general trend towards lower oxygenation of bottom waters across the MCE is accompanied by ongoing climate warming in combination with rising sea-level and the development of vast shallow epicontinental seas during the Middle and Late Cenomanian. These changes are proposed to have favoured the formation of warm and saline waters that may have contributed to intermediate- and deep-water masses at least in the restricted proto-North Atlantic and Tethyan Ocean basins, poor oxygenation of the Late Cenomanian sediments, and the changes in benthic foraminiferal assemblages across the MCE.