Stable carbon isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

The sediment cores 225514 and 225510 were recovered from 420 and 285 m water depth, respectively. They were investigated for their benthic foraminiferal delta13C during the last 500 years. Both cores were recovered from the southern flank of the Skagerrak. The delta13C values of Uvigerina mediterranea and other shallow infaunal species in both cores indicate that organic matter rain rates to the seafloor varied around a mean value until approximately AD 1950 after which they increased. This increase might result from changes in the North Atlantic Current System and a co-occurring persistently high North Atlantic Oscillation index state in the 1980s to 1990s, rather than from anthropogenic eutrophication. Using delta13C mean values of multiple species, we reconstruct delta13C gradients of dissolved inorganic carbon (DIC) within pore waters for the time periods AD 1500 to 1950 and AD 1950 to 2000. The calculated delta13CDIC ranges, interpreted as indicating total organic matter remineralization due to respiration, are generally bigger in Core 225514 than in Core 225510. Since mean delta13C values of U. mediterranea suggest that organic matter rain rates were similar at both locations, differences in total organic matter remineralization are attributed to differing oxygen availability. However, oxygen concentrations in the overlying bottom water masses are not likely to have differed significantly. Thus, we suggest that organic matter remineralization was controlled by oxygen availability within the sediments, reflecting strong differences in sedimentation rates at the two investigated core sites. Based on the assumptions that tests of benthic foraminiferal species inhabiting the same microhabitat depth should show equal delta13C values unless they are affected by vital effects and that Globobulimina turgida records pore water delta13CDIC, we estimate microhabitat-corrected vital effects for several species with respect to G. turgida: >0.7 per mil for Cassidulina laevigata, >1.3 per mil for Hyalinea balthica, and >0.7 per mil for Melonis barleeanus. Melonis zaandami seems to closely record pore water delta13CDIC.

Radiocarbon ages and 230Th data of five sediment cores from the Björn and Gardar Drift, North Atlantic

In locations of rapid sediment accumulation receiving substantial amounts of laterally transported material the timescales of transport and accurate quantification of the transported material are at the focus of intense research. Here we present radiocarbon data obtained on co-occurring planktic foraminifera, marine haptophyte biomarkers (alkenones) and total organic carbon (TOC) coupled with excess Thorium-230 (230Thxs) measurements on four sediment cores retrieved in 1649-2879 m water depth from two such high accumulation drift deposits in the Northeast Atlantic, Björn and Gardar Drifts. While 230Thxs inventories imply strong sediment focussing, no age offsets are observed between planktic foraminifera and alkenones, suggesting that redistribution of sediments is rapid and occurs soon after formation of marine organic matter, or that transported material contains negligible amounts of alkenones. An isotopic mass balance calculation based on radiocarbon concentrations of co-occurring sediment components leads us to estimate that transported sediment components contain up to 12% of fossil organic matter that is free of or very poor in alkenones, but nevertheless appears to consist of a mixture of fresh and eroded fossil material. Considering all available constraints to characterize transported material, our results show that although focussing factors calculated from bulk sediment 230Thxs inventories may allow useful approximations of bulk redeposition, they do not provide a unique estimate of the amount of each laterally transported sediment component. Furthermore, our findings provide evidence that the occurrence of lateral sediment redistribution alone does not always hinder the use of multiple proxies but that individual sediment fractions are affected to variable extents by sediment focussing.

Investigations on fossil bivalves and wood from Seymour Island, Antarctica

Quasi-periodic variation in sea-surface temperature, precipitation, and sea-level pressure in the equatorial Pacific known as the El Niño - Southern Oscillation (ENSO) is an important mode of interannual variability in global climate. A collapse of the tropical Pacific onto a state resembling a so-called 'permanent El Niño', with a preferentially warmed eastern equatorial Pacific, flatter thermocline, and reduced interannual variability, in a warmer world is predicted by prevailing ENSO theory. If correct, future warming will be accompanied by a shift toward persistent conditions resembling El Niño years today, with major implications for global hydrological cycles and consequent impacts on socioeconomic and ecological systems. However, much uncertainty remains about how interannual variability will be affected. Here, we present multi-annual records of climate derived from growth increment widths in fossil bivalves and co-occurring driftwood from the Antarctic peninsula that demonstrate significant variability in the quasi-biennial and 3-6 year bands consistent with ENSO, despite early Eocene (~50 Mya) greenhouse conditions with global average temperature -10 degrees higher than today. A coupled climate model suggests an ENSO signal and teleconnections to this region during the Eocene, much like today. The presence of ENSO variation during this markedly warmer interval argues for the persistence of robust interannual variability in our future greenhouse world.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Station characteristics and copepod fatty alcohol, fatty acid and lipid composition during MSM02/4 in Fram Strait

The biodiversity of pelagic deep-sea ecosystems has received growing scientific interest in the last decade, especially in the framework of international marine biodiversity initiatives, such as Census of Marine Life (CoML). While a growing number of deep-sea zooplankton species has been identified and genetically characterized, little information is available on the mechanisms minimizing inter-specific competition and thus allowing closely related species to co-occur in the deep-sea pelagic realm. Focussing on the two dominant calanoid copepod families Euchaetidae and Aetideidae in Fram Strait, Arctic Ocean, the present study strives to characterize ecological niches of co-occurring species, with regard to vertical distribution, dietary composition as derived from lipid biomarkers, and trophic level on the basis of stable isotope signatures. Closely related species were usually restricted to different depth layers, resulting in a multi-layered vertical distribution pattern. Thus, vertical partitioning was an important mechanism to avoid inter-specific competition. Species occurring in the same depth strata usually belonged to different genera. They differed in fatty acid composition and trophic level, indicating different food preferences. Herbivorous Calanus represent major prey items for many omnivorous and carnivorous species throughout the water column. The seasonal and ontogenetic vertical migration of Calanus acts as a short-cut in food supply for pelagic deep-sea ecosystems in the Arctic.

(Table 2) Radiocarbon data (fMC; fraction modern carbon and conventional 14C ages) of foraminifera, TOC and alkenones of cores ME0005A-24JC, Y69-71P and MC16

Paired radiocarbon measurements on haptophyte biomarkers (alkenones) and on co-occurring tests of planktic foraminifera (Neogloboquadrina dutertrei and Globogerinoides sacculifer) from late glacial to Holocene sediments at core locations ME0005-24JC, Y69-71P, and MC16 from the south-western and central Panama Basin indicate no significant addition of pre-aged alkenones by lateral advection. The strong temporal correspondence between alkenones, foraminifera and total organic carbon (TOC) also implies negligible contributions of aged terrigenous material. Considering controversial evidence for sediment redistribution in previous studies of these sites, our data imply that the laterally supplied material cannot stem from remobilization of substantially aged sediments. Transport, if any, requires syn-depositional nepheloid layer transport and redistribution of low-density or fine-grained components within decades of particle formation. Such rapid and local transport minimizes the potential for temporal decoupling of proxies residing in different grain-size fractions and thus facilitates comparison of various proxies for paleoceanographic reconstructions in this study area. Anomalously old foraminiferal tests from a glacial depth interval of core Y69-71P may result from episodic spillover of fast bottom currents across the Carnegie Ridge transporting foraminiferal sands towards the north.

Impacts of groundwater discharge at Myora Springs (North Stradbroke Island, Australia) on the phenolic metabolism of eelgrass, Zostera muelleri, and grazing by the juvenile rabbitfish, Siganus fuscescens

Myora Springs is one of many groundwater discharge sites on North Stradbroke Island (Queensland, Australia). Here spring waters emerge from wetland forests to join Moreton Bay, mixing with seawater over seagrass meadows dominated by eelgrass, Zostera muelleri. We sought to determine how low pH / high CO2 conditions near the spring affect these plants and their interactions with the black rabbitfish (Siganus fuscescens), a co-occurring grazer. In paired-choice feeding trials S. fuscescens preferentially consumed Z. muelleri shoots collected nearest to Myora Springs. Proximity to the spring did not significantly alter the carbon and nitrogen contents of seagrass tissues but did result in the extraordinary loss of soluble phenolics, including Folin-reactive phenolics, condensed tannins, and phenolic acids by ?87%. Conversely, seagrass lignin contents were, in this and related experiments, unaffected or increased, suggesting a shift in secondary metabolism away from the production of soluble, but not insoluble, (poly)phenolics. We suggest that groundwater discharge sites such as Myora Springs, and other sites characterized by low pH, are likely to be popular feeding grounds for seagrass grazers seeking to reduce their exposure to soluble phenolics.

(Table 2) Radiocarbon contents of TOC and alkenone samples

Radiocarbon age relationships between co-occurring planktic foraminifera, alkenones, and total organic carbon in sediments from the continental margins of southern Chile, northwest Africa, and the South China Sea were compared with published results from the Namibian margin. Age relationships between the sediment components are site-specific and relatively constant over time. Similar to the Namibian slope, where alkenones have been reported to be 1000-4500 years older than co-occurring foraminifera, alkenones were significantly (~1000 years) older than co-occurring foraminifera in the Chilean margin sediments. In contrast, alkenones and foraminifera were of similar age (within 2 sigma error or better) in the NW African and South China Sea sediments. Total organic matter and alkenone ages were similar off Namibia (age difference TOC alkenones: 200-700 years), Chile (100-450 years), and NW Africa (360-770 years), suggesting minor contributions of preaged terrigenous material. In the South China Sea, total organic carbon is significantly (2000-3000 years) older owing to greater inputs of preaged terrigenous material. Age offsets between alkenones and planktic foraminifera are attributed to lateral advection of organic matter. Physical characteristics of the depositional setting, such as seafloor morphology, shelf width, and sediment composition, may control the age of co-occurring sediment components. In particular, offsets between alkenones and foraminifera appear to be greatest in deposition centers in morphologic depressions. Aging of organic matter is promoted by transport. Age offsets are correlated with organic richness, suggesting that formation of organic aggregates is a key process.

Cretaceous radiolarians of the southern South Atlantic

Cretaceous radiolarians were recovered from subantarctic Atlantic calcareous submarine deposits from two of the seven sites drilled during ODP Leg 114 in 1987. Fairly well-preserved radiolarian assemblages were found in Hole 698A samples from the Northeast Georgia Rise, whereas assemblages with fair to good preservation were observed from Hole 700B in the East Georgia Basin. The assemblage compositions from both sites are rather low in diversity and are characterized by the dominance of Protoamphipyndax, Dictyomitra, and Stichomitra species, but lack zonal markers recognized from the midlatitude to low-latitude region. Assignment of a Maestrichtian age is based on co-occurring calcareous microfossils. This report constitutes the second such occurrence from the Atlantic sector of the Antarctic Ocean subsequent to the analysis of ODP Leg 113 materials from the Weddell Sea.

Impact of atmospheric pCO2, seawater temperature, and calcification rate on the delta 18O and delta 13C composition of echinoid calcite (Echinometra viridis)

The tropical echinoid Echinometra viridis was reared in controlled laboratory experiments at temperatures of approximately 20°C and 30°C to mimic winter and summer temperatures and at carbon dioxide (CO2) partial pressures of approximately 487 ppm-v and 805 ppm-v to simulate current and predicted-end-of-century levels. Spine material produced during the experimental period and dissolved inorganic carbon (DIC) of the corresponding culture solutions were then analyzed for stable oxygen (delta 18Oe, delta 18ODIC) and carbon (The tropical echinoid Echinometra viridis was reared in controlled laboratory experiments at temperatures of approximately 20°C and 30°C to mimic winter and summer temperatures and at carbon dioxide (CO2) partial pressures of approximately 487 ppm-v and 805 ppm-v to simulate current and predicted-end-of-century levels. Spine material produced during the experimental period and dissolved inorganic carbon (DIC) of the corresponding culture solutions were then analyzed for stable oxygen (delta18Oe, delta18ODIC) and carbon (delta13Ce, delta13CDIC) isotopic composition. Fractionation of oxygen stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta18O = delta18Oe - delta18ODIC) was significantly inversely correlated with seawater temperature but not significantly correlated with atmospheric pCO2. Fractionation of carbon stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (Delta delta13C = delta13Ce - delta13CDIC) was significantly positively correlated with pCO2 and significantly inversely correlated with temperature, with pCO2 functioning as the primary factor and temperature moderating the pCO2-delta13C relationship. Echinoid calcification rate was significantly inversely correlated with both delta18O and delta13C, both within treatments (i.e., pCO2 and temperature fixed) and across treatments (i.e., with effects of pCO2 and temperature controlled for through ANOVA). Therefore, calcification rate and potentially the rate of co-occurring dissolution appear to be important drivers of the kinetic isotope effects observed in the echinoid spines. Study results suggest that echinoid delta18O monitors seawater temperature, but not atmospheric pCO2, and that echinoid delta13C monitors atmospheric pCO2, with temperature moderating this relationship. These findings, coupled with echinoids' long and generally high-quality fossil record, supports prior assertions that fossil echinoid delta18O is a viable archive of paleo-seawater temperature throughout Phanerozoic time, and that delta13C merits further investigation as a potential proxy of paleo-atmospheric pCO2. However, the apparent impact of calcification rate on echinoid delta18O and delta13C suggests that paleoceanographic reconstructions derived from these proxies in fossil echinoids could be improved by incorporating the effects of growth rate.13Ce, delta13CDIC) isotopic composition. Fractionation of oxygen stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta18O = delta18Oe - delta18ODIC) was significantly inversely correlated with seawater temperature but not significantly correlated with atmospheric pCO2. Fractionation of carbon stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta13C = delta13Ce - delta13CDIC) was significantly positively correlated with pCO2 and significantly inversely correlated with temperature, with pCO2 functioning as the primary factor and temperature moderating the pCO2-delta13C relationship. Echinoid calcification rate was significantly inversely correlated with both delta18O and delta13C, both within treatments (i.e., pCO2 and temperature fixed) and across treatments (i.e., with effects of pCO2 and temperature controlled for through ANOVA). Therefore, calcification rate and potentially the rate of co-occurring dissolution appear to be important drivers of the kinetic isotope effects observed in the echinoid spines. Study results suggest that echinoid delta18O monitors seawater temperature, but not atmospheric pCO2, and that echinoid delta13C monitors atmospheric pCO2, with temperature moderating this relationship. These findings, coupled with echinoids' long and generally high-quality fossil record, supports prior assertions that fossil echinoid delta18O is a viable archive of paleo-seawater temperature throughout Phanerozoic time, and that delta13C merits further investigation as a potential proxy of paleo-atmospheric pCO2. However, the apparent impact of calcification rate on echinoid delta18O and delta13C suggests that paleoceanographic reconstructions derived from these proxies in fossil echinoids could be improved by incorporating the effects of growth rate.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Fork lengths, stomach contents and parasites of ninespine stickleback and arctic char in Iqalugaajuruluit Lake, Canada

Stable d13C and d15N isotopes, diet and parasites demonstrated that the prey consumed by ninespine stickleback Pungitius pungitius in a small lake on Baffin Island changed during the summer and also revealed intraspecific variation in their ecological niche. In July, there were differences in the diets of male and female ninespine stickleback as indicated by the stable isotopes, differences corroborated by the data on diet composition and the parasite fauna. Differences suggested that the sexes occupied different habitats during spawning. During July, females utilise the shallower littoral areas consuming zooplankton and benthic organisms, while males occupy deeper areas of the littoral zone feeding mainly on pelagic zooplankton. Parasite data support these observations as males had higher infections of copepod-transmitted parasites than females. There appeared to be no segregation of resources between males and females in late August, although the diet of both male and female ninespine stickleback shifted towards more benthic organisms, compared with July. Differences in d13C isotope, diet composition and infections of co-occurring parasites demonstrated that sympatric ninespine stickleback and Arctic char Salvelinus alpinus captured in the littoral zone occupied separate niches. Ninespine stickleback preyed mainly on zooplankton and chironomids, while Arctic char consumed a greater variety of prey items, including zooplankton and larger-sized prey such as insects and ninespine stickleback. The multifaceted approach improved our understanding of the trophic ecology of ninespine stickleback in southern Baffin Island and quantified resource use and dietary overlap with Arctic char.