Stable isotope and Cd/Ca ratios of Neogloboquadrina pachyderma in high-latitude sediments

Recent studies have stressed the role of high latitude nutrient levels and productivity in controlling the carbon isotopic composition of the deep sea and the CO2 content of the atmosphere. We undertook a study of the chemical composition of the polar planktonic foraminifer Neogloboquadrina pachyderma (s., sinistral coiling) from 30 late Holocene samples and 49 down core records from the high-latitude North and South Atlantic Oceans to evaluate the history of sea surface chemical change from glacial to interglacial time. Stable isotopic analysis of coretop samples from the Atlantic, Pacific and Southern Oceans shows no significant correlation between the delta13C of N. pachyderma and either delta13C or PO4 in seawater. Conversely, Cd/Ca ratios in planktonic foraminifera are consistent with the PO4 content of surface waters. The level of maximum glaciation (18,000 yr B.P.), identified by CLIMAP and delta18O, was chosen for mapping. Isopleths of delta18O on N. pachyderma (s.) in the North Atlantic reveal a pattern largely influenced by sea surface temperature (S.S.T.) and generally support the S.S.T. reconstruction of CLIMAP. Differences between the two suggest significantly lower salinity in North Atlantic surface waters at high latitudes than in lower latitudes. Down core delta13C records of N. pachyderma confirm that low delta13C values occurred in the northeast Atlantic during the latest glacial maximum (Labeyrie and Duplessy, 1985, doi:10.1016/0031-0182(85)90069-0). However, a map of delta13C for the 18,000 yr B.P. level for a much larger region in the North Atlantic shows that minimum N. pachyderma delta13C occurred in temperate waters. N. pachyderma delta13C decreased toward the southwest, reaching a minimum of -1 per mil at 37°N. Despite the variability seen in delta13C records of N. pachyderma, none of our cores show significant temporal variability in Cd/Ca. From the combined Cd/Ca and delta13C data we can see no evidence for an upwelling gyre in the eastern North Atlantic during the latest glacial maximum, nor evidence that the southern and northern oceans had significantly different levels of preformed nutrients than today.

(Table 3) Age determination of sediment cores from the SW Pacific Ocean

Eight- to ten-point depth profiles (from 1200 to 4800 m water depth) of oxygen and carbon isotopic values derived from benthic foraminifera, averaged over selected times in the past 160 ka, are presented. The data are from 10 sediment cores off eastern New Zealand, mainly North Chatham Rise. This lies under the Deep Western Boundary Current in the Southwest Pacific and is the main point of entry for several water masses into the Pacific Ocean. The benthic isotopic profiles are related to the structure of water masses at present and inferred for the past. These have retained a constant structure of Lower Circumpolar Deep Water-Upper Circumpolar Deep Water/North Pacific Deep Water-Antarctic Intermediate Water with no apparent changes in the depths of water mass boundaries between glacial and interglacial states. Sortable silt particle size data for four cores are also examined to show that the vigour of the inflow to the Pacific, while variable, appears to have remained fairly constant on average. Among the lowest Last Glacial Maximum values of benthic d13C in the world ocean (-1.03 per mil based on Cibicidoides wüllerstorfi) occurs here at ~2200 m. Comparable values occur in the Atlantic sector of the Southern Ocean, while those from the rest of the Pacific are distinctly higher, confirming that the Southern Ocean was the source for the unventilated/nutrient-enriched water seen here. Oxygen and carbon isotopic data are compatible with a glacial cold deep water mass of high salinity, but lower nutrient content (or better ventilated), below ~3500 m depth. This contrasts with the South Atlantic where unventilated/nutrient-enriched water extends all the way to the sea bed. Comparison with previous studies also suggests that the deeper reaches of the Antarctic Circumpolar Current below ~3500 m are not homogeneous all around the Southern Ocean, with the Kerguelen Plateau and/or the Macquarie-Balleny Ridges posing barriers to the eastward spread of the deepest low-d13C water out of the South Atlantic in glacials. These barriers, combined with inferred high density of bottom waters, restricted inter-basin exchange and allow three glacial domains dominated by bottom waters from Weddell Sea, Adelie Coast and Ross Sea to be defined. We suggest that the Ross Sea was the main source of the deep water entering the Pacific below ~3500 m.

(Table 1, 2) Foraminifera biometric data, and boron isotopic composition of Globigerinoides sacculifer of sediments from the Ontong-Java Plateau

Sediment samples from the Ontong-Java Plateau in the Pacific and the 90° east ridge in the Indian Ocean were used to investigate whether shell size and early diagenesis affect d11B of the symbiont-bearing planktonic foraminifer Globigerinoides sacculifer. In pristine shells from both study locations we found a systematic increase of d11B and Mg/Ca with shell size. Shells in the sieve size class 515-865 µm revealed d11B values +2.1 to +2.3 per mil higher than shells in the 250-380 µm class. This pattern is most likely due to differences in symbiont photosynthetic activity and its integrated effect on the pH of the foraminiferal microenvironment. We therefore suggest smaller individuals must live at approximately 50-100 m water depth where ambient light levels are lower. Using the empirical calibration curve for d11B in G. sacculifer, only shells larger than 425 µm reflect surface seawater pH. Partial dissolution of shells derived from deeper sediment cores was determined by shell weight analyses and investigation of the shell surface microstructure by scanning electron microscopy. The d11B in partially dissolved shells is up to 2 per mil lower relative to pristine shells of the same size class. In agreement with a relatively higher weight loss in smaller shells, samples from the Ontong-Java Plateau show a more pronounced dissolution effect than larger shells. On the basis of the primary size effect and potential postdepositional dissolution effects, we recommend the use of shells that are visually pristine and, in the case of G. sacculifer, larger than 500 ?m for paleoreconstructions.

Benthic foraminifera analysed in Skagerrak and Kattegat sediments

a) In der horizontalen Verbreitung sind die vorwiegend kalkschaligen Benthos-Foraminiferen im Untersuchungsgebiet auf zwei Faciesbereiche verteilt: 1. Eine sandige Facies mit stärkeren Temperatur- und Salzgehaltschwankungen; Wasseroberfläche t = 2O-17°C, Salzgehalt nie über 32 per mil, Meerestiefe 30 bis 92 m. 2. Schlick-Facies mit zum Teil feinsandigen Beimengungen. Temperatur- und Salzgehaltschwankungen sind geringer; Wasseroberfläche t = ca. 4O-15° C, Salzgehalt bis 34 per mil, Meerestiefe 135-548 m. b) Einige Stoßröhren-Proben (Station 18, 21, 27, 28) zeigen in ihrer vertikalen Verbreitung auffallende Faunenunterschiede. c) Im Profil des Lotkerns wechseln in der Foraminiferenfauna Bolivinen- und Cassidulinen-Nonioninen-Provinzen miteinander ab. Die Profile der beiden tiefsten Stoßröhren-Kerne (Station 23, 26; s. Tab. I) stimmen in ihrer Mikrofauna mit der des oberen Teils des Lotkerns (s. Tab. 4) überein. d) Die unter b und C angefuührten Faunenwechsel werden auf langperiodische Klimaerwärmungen im skandinavischen Raum und den damit verbundenen Anstieg des Meeresspiegels zurückgeführt. e) Der Lotkern kann mit Hilfe von Untersuchungsergebnissen aus seiner näheren Umgebung (Bohuslän, Oslofjord) nur bedingt in ein stratigraphisches, durch Megafossilien belegtes Schema eingefügt werden, da er nach unten durch die Mikrofauna keine echte Begrenzung aufweist. Durch die Einwanderung mehrerer Foraminiferenarten mit boreal-lusitanischer Verbreitung in die Untersuchungsgebiete wird der Lotkern in die Isocardia-Absätze (Atlanticum-oberes Subboreal) eingegliedert. f) Aus einer Tabelle von PRATJE(1940) kann entnommen werden, daß dieser Zeitabschnitt nach DE GEER etwa um 5000 v.Chr. beginnt. Danach beträgt die geringste Sedimentation, die in dem Kerngebiet nach dieser Zeitrechnung möglich ist, bei einer Eindringtiefe des Lots von 10 m ungefähr 1,40 m pro Jahrtausend. Wahrscheinlich wird dieses Maß etwas größer sein.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Effect of acidification on an Arctic phytoplankton community from Disko Bay, West Greenland

Long-term measurements (i.e. months) of in situ pH have not previously been reported from the Arctic; this study shows fluctuations between pH 7.5 and 8.3 during the spring bloom 2012 in a coastal area of Disko Bay, West Greenland. The effect of acidification on phytoplankton from this area was studied at both the community and species level in experimental pH treatments within (pH 8.0, 7.7 and 7.4) and outside (pH 7.1) in situ pH. The growth rate of the phytoplankton community decreased during the experimental acidification from 0.50 ± 0.01/day (SD) at pH 8.0 to 0.22 ± 0.01/day at pH 7.1. Nevertheless, the response to acidification was species-specific and divided into 4 categories: I, least affected; II, affected only at pH 7.1; III, gradually affected and IV, highly affected. In addition, the colony size and chain length of selected species were affected by the acidification. Our findings show that coastal phytoplankton from Disko Bay is naturally exposed to pH fluctuations exceeding the experimental pH range used in most ocean acidification studies. We emphasize that studies on ocean acidification should include in situ pH before assumptions on the effect of acidification on marine organisms can be made.

(Table 1) Determined and theoretical chemical composition of thaumasite of ODP Hole 135-841B

Hole 841B was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The hole penetrated a roughly 500-m-thick series of Miocene volcanic sediments with a number of basaltic to andesitic units (sills?) varying in thickness between 7 cm and 17 m. The volcanics are slightly to moderately altered and contain analcite, chabazite, natrolite-thompsonite, heulandite (?), prehnite, and quartz as secondary phases. In addition, thaumasite [Ca3Si(OH)6 * 12H2O](SO4)(CO3) was identified in the altered sequence. Sulfur isotope data of two thaumasite separates (+23.5 per mil and +21.1 per mil d34S) indicate a seawater origin of the sulfate sulfur. It is suggested that thaumasite is a product of low-temperature (<60 °C), seawater-derived CaCl2-rich fluids that were almost identical in composition to those presently circulating in the sub-seafloor.

(Table 1) Isotopic composition of organic compinents of DSDP Hole 24-231

Plant leaf wax hydrogen isotope (dDwax) reconstructions are increasingly being used to reconstruct hydrological change. This approach is based upon the assumption that variations in hydroclimatic variables, and in particular, the isotopic composition of precipitation (dDP), dominate dDwax. However modern calibration studies suggest that offsets between plant types may bias the dDwax hydrological proxy at times of vegetation change. In this study, I pair leaf wax analyses with published pollen data to quantify this effect and construct the first vegetation-corrected hydrogen isotopic evidence for precipitation (dDcorrP). In marine sediments from Deep Sea Drilling Program Site 231 in the Gulf of Aden spanning 11.4-3.8 Ma (late Miocene and earliest Pliocene), I find 77 per mil swings in dDwax that correspond to pollen evidence for substantial vegetation change. Similarities between dDP and dDcorrP imply that the hydrological tracer is qualitatively robust to vegetation change. However, computed vegetation corrections can be as large as 31 per mil indicating substantial quantitative uncertainty in the raw hydrological proxy. The resulting dDcorrP values quantify hydrological change and allow us to identify times considerably wetter than modern at 11.09, 7.26, 5.71 and 3.89 Ma. More generally, this novel interpretative framework builds the foundations of improved quantitative paleohydrological reconstructions with the dDwax proxy, in contexts where vegetation change may bias the plant-based proxy. The vegetation corrected paleoprecipitation reconstruction dDcorrP, represents the best available estimate as proof-of-concept, for an approach that I hope will be refined and more broadly applied.

(Table 1) Interstitial water geochemistry at DSDP Leg 84 Holes

On DSDP Leg 84, drilling was conducted at three gas-hydrate-bearing sites on the Middle America Trench slope off Costa Rica (Site 565) and off Guatemala (Sites 568 and 570). At Site 569, on the mid-slope off Guatemala, hydrates may be present, according to the seismic profile (GUA-13), although the pore-water composition does not provide clear evidence. Sites 566 and 567, on the lower Guatemala Trench slope, appear to be free of hydrates, except in fractures of serpentinite at the bottom of Hole 566. Hydrate-bearing Sites 565, 568, and 570 show the effects of hydrate decomposition on pore-water chemistry that have been established during previous drilling at Sites 496 and 497 on the Guatemala Trench slope. These include a chlorinity decrease and d18O increase downsection. The new results, however, reveal more complex relationships between the chlorinity decrease and d18O increase than previously recognized. At Site 565, d18O values decrease in the middle section of the hole, whereas chlorinity continues to decrease from the top to near the bottom of the hole. Early diagenetic alteration of volcanic glass is suggested as a mechanism for the unexpected minimum in the O-isotope curve. Multiple fractionation by the pore-water/hydrate system is required to explain d18O-values greater than 2.7 per mil at the bottom of Hole 568, because with a fractionation factor of alpha = 1.0027, this is the maximum figure a single-stage fractionation could produce. In situ water samples from hydrate zones in most cases failed to display the elevated salinities expected for the residual pore waters not involved in hydrate formation. This is probably because the in situ sampling device still allows a systematic pressure drop sufficient to trigger hydrate decomposition in the immediate vicinity of the sample port.

(Table 1) N-isotope record of planktonc foraminifera of sediment core MD02-2550C2

Constraining variations in marine N2-fixation over glacial-interglacial timescales is crucial for determining the role of the marine nitrogen cycle in modifying ocean productivity and climate, yet paleo-records from N2-fixation regions are sparse. Here we present new nitrogen isotope (d15N) records of bulk sediment and foraminifera test-bound (FB) nitrogen extending back to the last ice age from the oligotrophic Gulf of Mexico (GOM). Previous studies indicate a substantial terrestrial input during the last ice age and early deglacial, for which we attempt to correct the bulk sediment d15N using its observed relationship with the C/N ratio. Both corrected bulk and FB-d15N reveal a substantial glacial-to-Holocene decrease of d15N toward Holocene values of around 2.5 per mil, similar to observations from the Caribbean. This d15N change is most likely due to a glacial-to-Holocene increase in regional N2-fixation. A deglacial peak in the FB-d15N of thermocline dwelling foraminifera Orbulina universa probably reflects a whole ocean increase in the d15N of nitrate during deglaciation. The d15N of the surface dwelling foraminifera Globigerinoides ruber and the corrected bulk d15N show little sign of this deglacial peak, both decreasing from last glacial values much earlier than does the d15N of O. universa; this may indicate that G. ruber and bulk N reflect the euphotic zone signal of an early local increase in N2-fixation. Our results add to the evidence that, during the last ice age, the larger iron input from dust did not lead to enhanced N2-fixation in this region. Rather, the glacial-to-Holocene decrease in d15N is best explained by a response of N2-fixation within the Atlantic to the deglacial increase in global ocean denitrification.

Age model and sedimentation rate of core M174/KL11 (Table 1)

Stable isotope and faunal records from the central Red Sea show high-amplitude oscillations for the past 380,000 years. Positive delta18O anomalies indicate periods of significant salt buildup during periods of lowered sea level when water mass exchange with the Arabian Sea was reduced due to a reduced geometry of the Bab el Mandeb Strait. Salinities as high as 53 per mil and 55 per mil are inferred from pteropod and benthic foraminifera delta18O, respectively, for the last glacial maximum. During this period all planktonic foraminifera vanished from this part of the Red Sea. Environmental conditions improved rapidly after 13 ka as salinities decreased due to rising sea level. The foraminiferal fauna started to reappear and was fully reestablished between 9 ka and 8 ka. Spectral analysis of the planktonic delta18O record documents highest variance in the orbital eccentricity, obliquity, and precession bands, indicating a dominant influence of climatically - driven sea level change on environmental conditions in the Red Sea. Variance in the precession band is enhanced compared to the global mean marine climate record (SPECMAP), suggesting an additional influence of the Indian monsoon system on Red Sea climates.

Analyses of benthic and planktonic foraminifera during Marine Isotope Stage 5 of ODP Hole 172-1058C

Subtropical Gyres are an important constituent of the ocean-atmosphere system due to their capacity to store vast amounts of warm and saline waters. Here we decipher the sensitivity of the (sub)surface North Atlantic Subtropical Gyre with respect to orbital and millennial scale climate variability between ~140 and 70 ka, Marine Isotope Stage (MIS) 5. Using (isotope)geochemical proxy data from surface and thermocline dwelling foraminifers from Blake Ridge off the west coast of North America (ODP Site 1058) we show that the oceanographic development at subsurface (thermocline) level is substantially different from the surface ocean. Most notably, surface temperatures and salinities peak during the penultimate deglaciation (Termination II) and early MIS 5e, implying that subtropical surface ocean heat and salt accumulation might have resulted from a sluggish northward heat transport. In contrast, maximum thermocline temperatures are reached during late MIS 5e when surface temperatures are already declining. We argue that the subsurface warming originated from intensified Ekman downwelling in the Subtropical Gyre due to enhanced wind stress. During MIS 5a-d a tight interplay of the subtropical upper ocean hydrography to high latitude millennial-scale cold events can be observed. At Blake Ridge, the most pronounced of these high latitude cold events are related to surface warming and salt accumulation in the (sub)surface. Similar to Termination II, heat accumulated in the Subtropical Gyre probably due to a reduced Atlantic Meridional Overturning Circulation. Additionally, a southward shift and intensification of the subtropical wind belts lead to a decrease of on-site precipitation and enhanced evaporation, coupled to intensified gyre circulation. Subsequently, the northward advection of these warm and saline water likely contributed to the fast resumption of the overturning circulation at the end of these high latitude cold events.

Hydrocarbon analyses of submarine mud volcanoes (MV) in the Kumano forearc basin

Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2<250) and stable carbon isotopic compositions (d13C-CH4 >-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

(Table 1) Boron concentration and d11B values of interstitial water from IODP Holes 308-U1319A, U1320A, U1322B and U1324B

The Integrated Ocean Drilling Program Expedition 308 (IODP308) drilled normal-pressured sediments from the Brazos-Trinity Basin IV and over-pressured sediments from the Ursa Basin on the northern slope of the Gulf of Mexico. The interstitial water samples from the normal-pressured basin show B concentrations and B isotopic compositions ranging from 255 to 631 µM (0.6 to 1.5 times of seawater value) and from +29.1 to +42.7 per mil (relative to NIST SRM 951), respectively. A wider range is observed both for B concentrations (292 to 865 µM, 0.7 to 2.1 times of seawater value) and d11B values (+25.5 to +43.2 per mil) of the interstitial water in the over-pressured basin. The down-core distribution of B concentrations and d11B values in the interstitial waters are sensitive tracers for assessing various processes occurring in the sediment column, including boron adsorption/desorption reactions involving clay minerals and organic matter in sediments as well as fluid migration and mixing in certain horizons and in the sediment column. In the normal-pressured basin adsorption/desorption reactions in shallow sediments play the major role in controlling the B content and B isotopic composition of the interstitial water. In contrast, multiple processes affect the B content and d11B of the interstitial water in the over-pressured Ursa Basin. There, the stratigraphic level of the maxima of B and d11B correspond to seismic reflectors. The intruded fluids along the seismic reflector boundary from high to low-topography mix with local interstitial water. Fluid flow is inferred in the Blue Unit (a coarse sandstone layer, connecting the high- to low-pressured region) from the freshening of interstitial water in Ursa Basin Site U1322, and upward flow by the overpressure expels fluid from the overburden above the Blue Unit.

Temperatures, salinity, wind speed, grain sizes and foraminifera abundance in the Great Belt Channel, western Baltic Sea

The Great Belt, the largest inlet to the Baltic Sea, has a deep and well defined channel system. A distinct thermohaline layer at roughly 18 to 20 m of water depth separates the saltier and generally cooler deeper North Sea water from the brackish and warmer surface water. It is practically a current dominated area, with the strongest bottom currents due to prolonged west winds. The size and shape of the surface sediments and their grain size distributions show a close relationship with the prevailing hydrographical conditions. Southerly current marks predominate while northerly directions are confined to 10 to 14 m of water depth. The degree of bioturbation is highest in the uppermost sedimentary cover where practically all original stratification has been destroyed. Various bioturbate structures have been identified with the fauna. Coiling ratios of Ammonia beccarii (Linnaeus) have been successfully applied for correlation in the postglacial sediments of the early Littorina Transgression. The succession shows that in the Boreal brackish water conditions were probably followed by peat and limnic sediments as the sea regressed. With the Littorina Transgression, the sea again entered the area and high sedimentation rates resulted in the major deposits of the Great Belt. At least for the last 4000 years, sedimentation rates had been very low. Present day currents sweep out the sediments, mainly to the southern marginal areas.