Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Organic geochemistry of sediments from North Alex Mud Vulcano

Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of d13C ~-46.6 per mil VPDB and dD ~-228 per mil VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate-methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of d13C-CH4 ~-60 per mil VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

Chemistry of minerals from amphibole-chlorite veins of ODP Site 209-1270

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low d18O of altered plagiogranite veins (+3.0-4.2 per mil) and adjacent serpentinites (+ 2.6-3.7 per mil). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise.

(Table 1) Summary of sampling points described and main petrographic, morphological and geochemical characteristics

Targeted sampling on the Dolgovskoy Mound (northern Shatsky Ridge) revealed the presence of spectacular laterally extensive and differently shaped authigenic carbonates. The sampling stations were selected based on sidescan sonar and profiler images that show patchy backscatter and irregular and discontinuous reflections in the near subsurface. The interpretation of acoustic data from the top part of the mound supports the seafloor observations and the sampling that revealed the presence of a complex subsurface plumbing system characterized by carbonates and gas. The crusts sampled consist of carbonate cemented layered hemipelagic sedimentary Unit 1 associated with several centimetres thick microbial mats. Three different carbonate morphologies were observed: (a) tabular slabs, (b) subsurface cavernous carbonates consisting of void chambers up to 20 cm**3 in size and (c) chimney and tubular conduits vertically oriented or forming a subhorizontal network in the subsurface. The methanogenic origin of the carbonates is established based on visual observations of fluids seepage structures, 13C depletion of the carbonates (d13C varying between -36.7 per mil and -27.4 per mil), and by thin carbonate layers present within the thick microbial mats. Laboratory experiments with a Hele-Shaw cell were conducted in order to simulate the gas seepage through contrasting grain size media present on the seafloor. Combined petrography, visual observations and sandbox simulations allowed a characterization of the dynamics and the structures of the plumbing system in the near subsurface. Based on sample observations and the experiments, three observed morphologies of authigenic carbonates are interpreted, respectively, as (a) Darcian porous flow through the finely laminated clayey/coccolith-rich layers, (b) gas accumulation chambers at sites where significant fluid escape was impeded by thicker clayey layers forming the laminated Unit1 and (c) focussed vertical fluid venting and subhorizontal migration of overpressured fluids released from (b). The Hele-Shaw cell experiments represent a promising tool for investigating shallow fluid flow pathways in marine systems.

Carbon and oxygen isotopic compositions of Cibicidoides spp. and fine fraction separates (<10 µm) from ODP Holes 113-689B, 119-738B, and 120-748B

A prominent middle Eocene warming event is identified in Southern Ocean deep-sea cores, indicating that long-term cooling through the middle and late Eocene was not monotonic. At sites on Maud Rise and the Kerguelen Plateau, a distinct negative shift in d18O values (~1.0 per mil) is observed ca. 41.5 Ma. This excursion is interpreted as primarily a temperature signal, with a transient warming of 4°C over 600 k.y. affecting both surface and middle-bathyal deep waters in the Indian-Atlantic region of the Southern Ocean. This isotopic event is designated as the middle Eocene climatic optimum, and is interpreted to represent a significant climatic reversal in the midst of middle to late Eocene deep-sea cooling. The lack of a significant negative carbon isotope excursion, as observed during the Paleocene-Eocene thermal maximum, and the gradual rate of high-latitude warming suggest that this event was not triggered by methane hydrate dissociation. Rather, a transient rise in pCO2 levels is suspected, possibly as a result of metamorphic decarbonation in the Himalayan orogen or increased ridge/arc volcanism during the late middle Eocene.

Assemblages and isotopic signals of modern ostracodes and host waters from Patagonia, Argentine

Ostracode species assemblages and stable oxygen and carbon isotope ratios of living and recent ostracodes, together with delta18O and delta13C_DIC values of host water samples, provide a first data set that characterizes a wide range of modern aquatic environments in the Laguna Cari-Laufquen (41°S, 68 - 69°W) and the Lago Cardiel area (48 - 49°S, 70 - 71°W) in Patagonia, Argentina. This data set will ultimately be used to interpret and calibrate data acquired from lake sediment cores with the goal of reconstructing past climate. Species assemblages and isotope values can be assigned to three groups; (1) springs, seeps and streams, (2) permanent ponds and lakes, and (3) ephemeral ponds and lakes. Springs, seeps and streams are characterized by Darwinula sp., Heterocypris incongruens, Eucypris fontana, Amphicypris nobilis and Ilyocypris ramirezi. Ostracode and water isotope values range between -13 and -5 per mil for oxygen, and between -15 and -3 per mil for carbon. They are the most negative of the entire sample set, reflecting ground water input with little or no evaporative enrichment. Limnocythere patagonica, Eucypris labyrinthica, Limnocythere sp. and Eucypris aff. fontana are typical species of permanent ponds and lakes. Isotope values indicate high degree of evaporation of lake waters relative to feeder springs and streams and range between -7 and +5 per mil for oxygen, and -5 and +4 per mil for carbon. Limnocythere rionegroensis is the dominant species in ephemeral ponds and lakes. These systems display the most enriched isotope values in both ostracodes and host waters, extending from -5 to +7 per mil for oxygen, and from -5 to +6 per mil for carbon. Living ostracodes show a positive offset from equilibrium values of up to 2 per mil for oxygen. Carbon-isotope values are up to 6? more negative than equilibrium values in highly productive pools. Comparison of ostracode and host water isotope signals permits assessment of the life span of the aquatic environments. Valves from dead ostracodes collected from ephemeral ponds and lakes show a wide scatter with each sample providing a snapshot of the seasonal history of the host water. The presence of the stream species Ilyocypris ramirezi and a wide range of ostracode isotope values suggest that ephemeral ponds and lakes are fed by streams during spring run-off and seasonally dry. A temporary character is also indicated by Heterocypris incongruens, a drought-resistant species that occupies most springs and seeps. In addition, Limnocythere rionegroensis has adjusted its reproduction strategies to its environment. Whereas only females were collected in fresh host waters, males were found in ephemeral ponds and lakes with higher solute content. Sexual reproduction seems to be the more successful reproduction strategy in high and variable salinities and seasonal droughts. The temporary character of the aquatic environments shows that the availability of meteoric water controls the life span of host waters and underlines the sensitivity of the area to changes in precipitation.

Stable oxygen and carbon isotope compositions of Campanian grainstones and rudstones

Petrographic descriptions and stable oxygen and carbon isotope compositions of microsamples of Campanian-age sediment gravity-flow deposits from Northeast Providence Channel, Bahamas, indicate deep-marine cementation of shallow-marine skeletal grains that were transported to the channel during the Late Cretaceous. Shallow-marine components are represented by mollusks, especially rudists, and shallow-water benthic foraminifers as well as sparse echinoderm and algal grains. The sole evidence of diagenesis in shallow-marine environments consists of micrite envelopes around skeletal grains. Shallow-marine skeletal grains have mean stable isotope values of -3.1 per mil d18O and +2.6 per mil d13C. The d18O values are consistent with precipitation in equilibrium with warm (20°-30°C), shallow-marine water. Deep-marine components are represented by equant calcite spar cements and rip-up clasts of slope sediments. Spar cements, exhibiting hexagonal morphology with scalenohedral terminations, most commonly occur as thin isopachous linings in the abundant porosity. Deep-marine cements have mean stable isotope values of - 1.1 per mil d18O and +2.7 per mil d13C. Deep-marine cements are 18O-enriched relative to shallow-marine skeletal grains, consistent with precipitation in equilibrium with colder (10°-20°C), deep-marine waters. The cement .source during lithification appears to have been dissolution of aragonite and high-magnesium calcite skeletal grains, which made up part of the transported sediment. Interbedded periplatform ooze remains uncemented, or poorly cemented, probably because of lower permeability. Equant spar cements that occur in gravity-flow deposits recovered from Hole 634A have stable isotope compositions similar to spars in Lower and mid-Cretaceous shallow-water limestones exposed on the Bahama Escarpment, to Campanian-Paleocene deep-marine hardgrounds recovered during DSDP Leg 15 in the Caribbean, and to spars in Aptian-Albian talus deposits at the base of the Campeche Escarpment recovered during DSDP Leg 77.

Tab. 1 Mole % CO2 and 13C values of CO2 at baseline and at the final monitoring event for the eight observation wells

During CO2 storage operations in mature oilfields or saline aquifers it is desirable to trace the movement of injected CO2 for verification and safety purposes. We demonstrate the successful use of carbon isotope abundance ratios for tracing the movement of CO2 injected at the Cardium CO2 Storage Monitoring project in Alberta between 2005 and 2007. Injected CO2 had a d13C value of -4.6±1.1 per mil that was more than 10 per mil higher than the carbon isotope ratios of casing gas CO2 prior to CO2 injection with average d13C values ranging from -15.9 to -23.5 per mil. After commencement of CO2 injection, d13C values of casing gas CO2 increased in all observation wells towards those of the injected CO2 consistent with a two-source end-member mixing model. At four wells located in a NE-SW trend with respect to the injection wells, breakthrough of injected CO2 was registered chemically (>50 mol % CO2) and isotopically 1-6 months after commencement of CO2 injection resulting in cumulative CO2 fluxes exceeding 100000 m**3 during the observation period. At four other wells, casing gas CO2 contents remained below 5 mol % resulting in low cumulative CO2 fluxes (<2000 m**3) throughout the entire observation period, but carbon isotope ratios indicated contributions between <30 and 80% of injected CO2. Therefore, we conclude that monitoring the movement of CO2 in the injection reservoir with geochemical and isotopic techniques is an effective approach to determine plume expansion and to identify potential preferential flow paths provided that the isotopic composition of injected CO2 is constant and distinct from that of baseline CO2.

Living benthic foraminifers in bottom sediments of the southeastern Kandalaksha Bay (White Sea)

Analysis of composition and distribution of benthic foraminifers in six samples of bottom sediments obtained in the southeast Kandalaksha Bay of the White Sea at water depths of 20 to 155 m revealed their dependence on lithology and different hydrological characteristics. It is shown that living foraminifers populating relatively shallow areas of the bay (20-60 m), which are bathed by seasonally warmed intermediate water with temperature 0.7-1.5°C and salinity 26 per mil, are characterized by high abundance (250-750 specimens/10 ccm of wet sediment) and prevalence of agglutinated species (Eggerella advena, Recurvoides turbinatus, and others). Deeper (155 m) where cold and relatively saline deep water occurs (-1.4°C, 29.5 per mil), abundance is an order lower (30 specimens/10 ccm) and is dominated by calcareous taxa Cassidulina reniforme, an Arctic cold resistant species.

Planktonic foraminifera fluxes and stable isotope ratios in the Irminger Sea

Past water column stratification can be assessed through comparison of the d18O of different planktonic foraminiferal species. The underlying assumption is that different species form their shells simultaneously, but at different depths in the water column. We evaluate this assumption using a sediment trap time-series of Neogloboquadrina pachyderma (s) and Globigerina bulloides from the NW North Atlantic. We determined fluxes, d18O and d13C of shells from two size fractions to assess size-related effects on shell chemistry and to better constrain the underlying causes of isotopic differences between foraminifera in deep-sea sediments. Our data indicate that in the subpolar North Atlantic differences in the seasonality of the shell flux, and not in depth habitat or test size, determine the interspecies Delta d18O. N. pachyderma (s) preferentially forms from early spring to late summer, whereas the flux ofG. bulloides peaks later in the season and is sustained until autumn. Likewise, seasonality influences large and small specimens differently, with large shells settling earlier in the season. The similarity of the seasonal d18O patterns between the two species indicates that they calcify in an overlapping depth zone close to the surface. However, their d13C patterns are markedly different (>1 per mil). Both species have a seasonally variable offset from d13CDIC that appears to be governed primarily by temperature, with larger offsets associated with higher temperatures. The variable offset from d13CDIC implies that seasonality of the flux affects the fossil d13C signal, which has implications for reconstruction of the past oceanic carbon cycle.

Nitrogen isotopic and opal record of sediments in the Gulf of California

High-resolution records of the nitrogen isotopic composition of organic matter (d15Norg), opal content, and opal accumulation rates from the central Gulf of California reveal large and abrupt variations during deglaciation and gradual Holocene changes coincident with climatic changes recorded in the North Atlantic. Homogenous sediments with relatively low d15Norg values and low opal content were deposited at the end of the last glacial period, during the Younger-Dryas event, and during the middle to late Holocene. In contrast, laminated sediments deposited in the two deglacial stages are characterized by very high d15Norg values (>14 per mil) and opal accumulation rates (29-41 mg/cm**2/yr). Abrupt shifts in d15Norg were driven by widespread changes in the extent of suboxic subsurface waters supporting denitrification and were amplified in the central gulf record due to variations in upwelling, vertical mixing, and/or the latitudinal position of the Intertropical Convergence Zone.

Biphytane and stable carbon isotopic values of sugars and glycerol from ODP Hole 204-1245D and 201-1229A

The membrane lipids diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2G-GDGTs) in marine subsurface sediments are believed to originate from uncultivated benthic archaea, yet the production of 2G-GDGTs from subseafloor samples has not been demonstrated in vitro. In order to validate sedimentary biosynthesis of 2G-GDGTs, we performed a stable carbon isotope probing experiment on a subseafloor sample with six different 13C-labelled substrates (bicarbonate, methane, acetate, leucine, glucose and Spirulina platensis biomass). After 468 days of anoxic incubation, only glucose and S. platensis resulted in label uptake in lipid moieties of 2G-GDGTs, indicating incorporation of carbon from these organic substrates. The hydrophobic moieties of 2G-GDGTs showed minimal label incorporation, with up to 4 per mil 13C enrichment detected in crenarchaeol-derived tricyclic biphytane from the S. platensis-supplemented slurries. The 2G-GDGT-derived glucose or glycerol moieties also showed 13C incorporation (Dd13C = 18 - 38 per mil) in the incubations with glucose or S. platensis, consistent with a lipid salvage mechanism utilized by marine benthic archaea to produce new 2G-GDGTs. The production rates were nevertheless rather slow, even when labile organic matter was supplied. The 2G-GDGT turnover times of 1700 - 20 500 years were much longer than those estimated for subseafloor microbial communities, implying that sedimentary 2G-GDGTs as biomarkers of benthic archaea are cumulative records of past and present generations.

(Table 1) Oxygen and carbon isotope ratios of benthic foraminifera of DSDP Holes 12-119 and 48-401

We present here oxygen and carbon isotopic records of Eocene to Oligocene benthic foraminifera from two Bay of Biscay Deep Sea Drilling Project (DSDP) sites (119 and 401). d18O of benthic foraminifera increases 1.9 per mil from a middle Eocene minimum (Zones P10-P11) to an earliest Oligocene maximum (Zone NP21). Approximately 1.4 per mil of the increase in benthic foraminiferal d18O occurs during the late Eocene to earliest Oligocene (Zones P15/16-NP21). Previous results from other North Atlantic DSDP sites (400A and 398) have significantly lower d18O values of benthic foraminifera, some by as much as 2 per mil (Vergnaud-Grazzini et al., 1978; 1989, doi:10.2973/dsdp.proc.48.119.1979; Vergnaud-Grazzini, 1979, doi:10.2973/dsdp.proc.47-2.117.1979 ). We believe that these differences result from diagenetic alteration of the sediments in the deeper-buried Sites 400A and 398.

X-ray fluorescence (XRF) scannings and grain size analysis at sites in the Gulf of Cádiz

Contourites in the Gulf of Cádiz preserve a unique archive of Mediterranean Outflow Water (MOW) variability over the past 5.3 Ma. In our study we investigate the potential of geochemical data obtained by XRF scanning to decipher bottom current processes and paleoclimatic evolution at two different sites drilled through contourite deposits in the northern Gulf of Cadiz: Site U1387, which is bathed by the upper MOW core, and Site U1389, located more proximal to the Straits of Gibraltar. The lack of major downslope transport at both locations during the Pleistocene makes them ideal locations for the purpose of our study. The results indicate that the Zr/Al ratio, representing the relative enrichment of heavy minerals (zircon) over less dense alumosilicates under strong bottom current flow, is the most useful indicator for a semi-quantitative assessment of current strength. While most elements are biased by current-related processes, the bromine record, representing organic content, preserves the most pristine climate signal rather independent of grain size changes. Hence, Br can be used for chronostratigraphy and site-to-site correlation in addition to stable isotope stratigraphy. Based on these findings we reconstructed MOW variability for Marine Isotope Stages 1-5 using the Zr/Al ratio from Site U1387. The results reveal abrupt, millennial-scale variations of MOW strength during Greenland Stadials (GS) and Interstadials (GI) with strong MOW during GS and glacial Terminations and a complex behavior during Heinrich Stadials. Millennial-scale variability persisting during periods of poorly expressed GS/GI cyclicities implies a strong internal oscillation of the Mediterranean/North Atlantic climate system.

Abundance of phytoplankton, heterotrophic nanoflagellates and bacteria through the water column at time series station L4 in the Western English Channel. 2007-2011

The marine laboratories in Plymouth have sampled at two principle sites in the Western English Channel for over a century in open-shelf (station E1; 50° 02'N, 4° 22'W) and coastal (station L4; 50° 15'N, 4° 13'W) waters. These stations are seasonally stratified from late-April until September, and the variable biological response is regulated by subtle variations in temperature, light, nutrients and meteorology. Station L4 is characterized by summer nutrient depletion, although intense summer precipitation, increasing riverine input to the system, results in pulses of increased nitrate concentration and surface freshening. The winter nutrient concentrations at E1 are consistent with an open-shelf site. Both stations have a spring and autumn phytoplankton bloom; at station E1, the autumn bloom tends to dominate in terms of chlorophyll concentration. The last two decades have seen a warming of around 0.6°C per decade, and this is superimposed on several periods of warming and cooling over the past century. In general, over the Western English Channel domain, the end of the 20th century was around 0.5°C warmer than the first half of the century. The warming magnitude and trend is consistent with other stations across the north-west European Shelf and occurred during a period of reduced wind stress and increased levels of insolation (+20%); these are both correlated with the larger scale climatic forcing of the North Atlantic Oscillation.