Geochemistry, carbon isotope ratio and radiocarbon ages of sediment core GIK1093-2 from Bornholm Basin, Baltic Sea

Concentrations of Cd, Pb, Zn, Cu, Co, Ni, Fe, and Al203, water content, the amounts of organic carbon, the ratio of 13C/12C and the 14C-activity of the organic fraction were determined with sediment depth from a 34 cm long box-core from the Bornholm Basin (Baltic Sea). The average sedimentation rate was 2.4 mm/yr. The upper portion of the core contained increasing amounts of 14C-inactive organic carbon, and above 3 cm depth, man-made 14C from atomic bomb tests. The concentrations of the heavy metals Cd, Pb, Zn, and Cu increase strongly towards the surface, while other metals, as Fe, Ni and Co remain almost unchanged. This phenomenon is attributed to anthropogenic influences. A comparison of the Kieler Bucht, the Bornholm and the Gotland Basins shows that today the anthropogenic addition of Zn is about 100 mg/m**2 yr in all three basins. The beginning of this excess of Zn, however, is delayed by about 20 years in, the Bornholm Basin and by about 40 years in the Gotland Basin. It is suggested that SW-NE transport of these anthropogenically mobilized metals may be related to periodic bottom water renewal in the Baltic Sea sedimentary basins.

Bulk sediment and diatom silica carbon isotope composition from Antarctic coastal marine sediments

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. d13C from diatom carbon (d13C(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on d13C(diatom). Numerous variables can influence d13C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO2 availability). Here we compare d13C(diatom) and d13C(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between d13C(diatom) and d13C(TOC), to (ii) identify biological and environmental controls on d13C(diatom) and d13C(TOC), and to (iii) discuss d13C(diatom) as a proxy for environmental and climate reconstructions. The records show individual d13C(diatom) and d13C(TOC) characteristics, which indicates that d13C is not primarily controlled by regional climate or atmospheric CO2 concentration. Since the inlets vary in water depths offsets in d13C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in d13C(diatom) and d13C(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in d13C(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted d13C(diatom) values (1-4 per mil) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in d13C(diatom), which is in the same order of magnitude. d13C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and d13C is of strongly local nature.

Organic carbon concentrations and isotope ratios of sediments from the Laptev Sea

Stable carbon isotope ratios in the organic fraction of surface sediments from the Laptev Sea shelf were analyzed in order to study the modern distribution pattern of terrestrial organic matter. The delta13Corg signature of the surface sediments range from -26.6? near the coastal margin to -22.8? in the north towards the outer shelf. Characterizing the possible sources of organic matter by their delta13Corg signature reveals that the terrestrial influence reaches further north in the eastern than in the western Laptev Sea. Downcore records of the delta13Corg, measured on three AMS 14C-dated cores from water depths between 46 and 77 m, specify the spatial and temporal changes in the deposition of terrestrial organic matter on the Laptev Sea shelf during the past 12.7 ka. The major depositional changes of terrestrial organic matter occurred between 11 and 7 ka and comprised the main phase of the southward retreat of the coastline and of the river depocenters due to the postglacial sea level rise.

Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.

Exploring the potential of clumped isotope thermometry on coccolith-rich sediments as a sea surface temperature proxy

Understanding past changes in sea surface temperatures (SSTs) is crucial; however, existing proxies for reconstructing past SSTs are hindered by unknown ancient seawater composition (foraminiferal Mg/Ca and d18O), or reflect subsurface temperatures (TEX86) or have a limited applicable temperature range (Uk'37). We examine clumped isotope (D47) thermometry to fossil coccolith-rich material as an SST proxy, as clumped isotopes are independent of original seawater composition and applicable to a wide temperature range and coccolithophores are widespread and dissolution resistant. The D47-derived temperatures from <63, <20, <10 and 2-5 µm size fractions of two equatorial Pacific late Miocene-early Pliocene sediment samples (c1; c2) range between ~18-29 {degree sign}C, with c1 temperatures consistently above c2. Removing the >63 µm fraction removes most non-mixed layer components; however, the D47-derived temperatures display an unexpected slight decreasing trend with decreasing size fraction. This unexpected trend could partly arise because larger coccoliths (5-12 µm) are removed during the size fraction separation process. The c1 and <63 µm c2 D47-derived temperatures are comparable to concurrent Uk'37 SSTs. The <20, <10 and 2-5 µm c2 D47-derived temperatures are consistently cooler than expected. The D47-Uk'37 temperature offset is probably caused by abiotic/diagenetic calcite present in the c2 2-5 µm fraction (~53% by area), which potentially precipitated at bottom water temperatures of ~6 {degree sign}C . Our results indicate that clumped isotopes on coccolith-rich sediment fractions have potential as an SST proxy, particularly in tropical regions, providing that careful investigation of the appropriate size fraction for the region and timescale is undertaken.

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. delta 13C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between delta 13C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. delta 15N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.

Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

(Table S1) Carbon and oxygen isotope values, and Mn and Sr concentrations of Early Jurassic sediments

For much of the Mesozoic record there has been an inconclusive debate on the possible global significance of isotopic proxies for environmental change and of sequence stratigraphic depositional sequences. We present a carbon and oxygen isotope and elemental record for part of the Early Jurassic based on marine benthic and nektobenthic molluscs and brachiopods from the shallow marine succession of the Cleveland Basin, UK. The invertebrate isotope record is supplemented with carbon isotope data from fossil wood, which samples atmospheric carbon. New data elucidate two major global carbon isotope events, a negative excursion of ~2 per mil at the Sinemurian-Pliensbachian boundary, and a positive excursion of ~2 per mil in the Late Pliensbachian. The Sinemurian-Pliensbachian boundary event is similar to the slightly younger Toarcian Oceanic Anoxic Event and is characterized by deposition of relatively deepwater organic-rich shale. The Late Pliensbachian strata by contrast are characterized by shallow marine deposition. Oxygen isotope data imply cooling locally for both events. However, because deeper water conditions characterize the Sinemurian-Pliensbachian boundary in the Cleveland Basin the temperature drop is likely of local significance; in contrast a cool Late Pliensbachian shallow seafloor agrees with previous inference of partial icehouse conditions. Both the large-scale, long-term and small-scale, short-duration isotopic cycles occurred in concert with relative sea level changes documented previously from sequence stratigraphy. Isotope events and the sea level cycles are concluded to reflect processes of global significance, supporting the idea of an Early Jurassic in which cyclic swings from icehouse to greenhouse and super greenhouse conditions occurred at timescales from 1 to 10 Ma.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

Organic carbon isotope ratios of sea surface sediments and sea-ice from the Amerasian Continental shelf

Organic matter origins are inferred from carbon isotope ratios (delta13C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in delta13C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment delta13C, OC/N, and delta15N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C3 plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C4 and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment delta13C values (-16.5 to -13.6 per mil) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO2 and pCO2 in the Arctic Basin halocline.

(Appendix A) Oxygen and carbon isotope results of detrital carbonate grains of Heinrich layers from HU90-013-028 and IODP Sites 303-U1302/U1303/U1308 in the North Atlantic Ocean

We report oxygen and carbon isotope results of detrital carbonate grains from Heinrich layers at three sites in the North Atlantic located along a transect from the Labrador Sea to the eastern North Atlantic. Oxygen isotopic values of individual detrital carbonate grains from six Heinrich layers at all sites average - 5.6 ppm ± 1.5 ppm (1sigma; n = 166), reflecting values of dolomitic limestone derived from source areas in northeastern Canada. The d18O of bulk carbonate at Integrated Ocean Drilling Program (IODP) Site U1308 (re-occupation of Deep Sea Drilling Project (DSDP) Site 609) in the eastern North Atlantic records the proportion of detrital to biogenic carbonate and d18O decreases to - 5 ppm during Heinrich (H) events 1, 2, 4 and 5 relative to a background value of ~ 1 to 2 ppm for biogenic carbonate. Bulk d18O also decreases during H3 and H6 but only attains values of - 1ppm, indicating either a greater proportion of biogenic-to-detrital carbonate or a different source. Because the d18O of detrital carbonate is ~ 9 ppm lower than foraminifer carbonate, any fine-grained detrital carbonate not removed from the inner test chambers will lower foraminifer d18O. We conclude bulk carbonate d18O is a sensitive proxy for detrital carbonate and may be useful for identifying Heinrich layers in cores within and near the margins of the North Atlantic ice-rafted detritus (IRD) belt.

Carbon and oxygen isotope ratios of Selinde River, southeastern Siberian platform

Carbon isotopic data from the Selinde section in the southeastern part of the Siberian platform area are correlated with the reference isotopic profile from the Lower Cambrian stratotype sections of the Lena Aldan region, but also show additional d13C excursions unrecognized there. The chemostratigraphic correlation suggests that the geological and fossil record of the lower Pestrotsvet Formation in the Selinde section has a deeper history than the stratotype region. This conclusion is important for both constraining the age of the earliest Cambrian marine transgression on the Siberian platform and providing a clearer understanding of the pace and order of early Cambrian geochemical and biological events.