On the role of circulation and mixing in the ventilation of oxygen minimum zones with a focus on the eastern tropical North Atlantic

Ocean observations carried out in the framework of the Collaborative Research Center 754 (SFB 754) "Climate-Biogeochemistry Interactions in the Tropical Ocean" are used to study (1) the structure of tropical oxygen minimum zones (OMZs), (2) the processes that contribute to the oxygen budget, and (3) long-term changes in the oxygen distribution. The OMZ of the eastern tropical North Atlantic (ETNA), located between the well-ventilated subtropical gyre and the equatorial oxygen maximum, is composed of a deep OMZ at about 400 m depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m depth with lowest oxygen concentrations in proximity to the coastal upwelling region off Mauritania and Senegal. The oxygen budget of the deep OMZ is given by oxygen consumption mainly balanced by the oxygen supply due to meridional eddy fluxes (about 60%) and vertical mixing (about 20%, locally up to 30%). Advection by zonal jets is crucial for the establishment of the equatorial oxygen maximum. In the latitude range of the deep OMZ, it dominates the oxygen supply in the upper 300 to 400 m and generates the intermediate oxygen maximum between deep and shallow OMZs. Water mass ages from transient tracers indicate substantially older water masses in the core of the deep OMZ (about 120-180 years) compared to regions north and south of it. The deoxygenation of the ETNA OMZ during recent decades suggests a substantial imbalance in the oxygen budget: about 10% of the oxygen consumption during that period was not balanced by ventilation. Long-term oxygen observations show variability on interannual, decadal and multidecadal time scales that can partly be attributed to circulation changes. In comparison to the ETNA OMZ the eastern tropical South Pacific OMZ shows a similar structure including an equatorial oxygen maximum driven by zonal advection, but overall much lower oxygen concentrations approaching zero in extended regions. As the shape of the OMZs is set by ocean circulation, the widespread misrepresentation of the intermediate circulation in ocean circulation models substantially contributes to their oxygen bias, which might have significant impacts on predictions of future oxygen levels.

Planktic foraminiferal Mg/Ca and oxygen isotopes, plus estimated d18Oseawater and ice volume corrected d18Oseawater for the past 35000 years of sediment core GeoB10069-3

Evidence from geologic archives suggests that there were large changes in the tropical hydrologic cycle associated with the two prominent northern hemisphere deglacial cooling events, Heinrich Stadial 1 (HS1; ~19 to 15 kyr BP; kyr BP = 1000 yr before present) and the Younger Dryas (~12.9 to 11.7 kyr BP). These hydrologic shifts have been alternatively attributed to high and low latitude origin. Here, we present a new record of hydrologic variability based on planktic foraminifera-derived d18O of seawater (d18Osw) estimates from a sediment core from the tropical Eastern Indian Ocean, and using 12 additional d18Osw records, construct a single record of the dominant mode of tropical Eastern Equatorial Pacific and Indo-Pacific Warm Pool (IPWP) hydrologic variability. We show that deglacial hydrologic shifts parallel variations in the reconstructed interhemispheric temperature gradient, suggesting a strong response to variations in the Atlantic Meridional Overturning Circulation and the attendant heat redistribution. A transient model simulation of the last deglaciation suggests that hydrologic changes, including a southward shift in the Intertropical Convergence Zone (ITCZ) which likely occurred during these northern hemisphere cold events, coupled with oceanic advection and mixing, resulted in increased salinity in the Indonesian region of the IPWP and the eastern tropical Pacific, which is recorded by the d18Osw proxy. Based on our observations and modeling results we suggest the interhemispheric temperature gradient directly controls the tropical hydrologic cycle on these time scales, which in turn mediates poleward atmospheric heat transport.

Strontium concentrations and isotopic compositions of anhydrites from the TAG active mound

Sr isotope analyses have been conducted on anhydrite samples from the TAG (Trans-Atlantic Geotraverse) active hydrothermal mound (26°08?N, Mid-Atlantic Ridge) that have previously been shown to exhibit two distinct patterns of REE behavior when normalized to TAG end-member hydrothermal fluid. Despite differences in REE patterns, the Sr isotope data indicate that all the anhydrites precipitated from fluids with a similar range of hydrothermal fluid and seawater components, and all but one were seawater-dominated (52%-75%). Speciation calculations using the EQ3/6 software package for geochemical modeling of aqueous systems suggest that the REE complexation behavior in different fluid mixing scenarios can explain the variations in the REE patterns. Anhydrites that exhibit relatively flat REE patterns [(La_bs)/(Yb_bs) = 0.8-2.0; subscript bs indicates normalization to end-member black smoker hydrothermal fluid] and a small or no Eu anomaly [(Eu_bs)/(Eu*_bs) = 0.8-2.0] are inferred to have precipitated from mixes of end-member hydrothermal fluid and cold seawater. REE complexes with hard ligands (e.g., fluoride and chloride) are less stable at low temperatures and trivalent Eu has an ionic radius similar to that of Ca2+ and the other REE, and so they behave coherently. In contrast, anhydrites that exhibit slight LREE-depletion [(La_bs)/(Yb_bs) = 0.4-1.4] and a distinct negative anomaly [(Eu_bs)/(Eu*_bs) = 0.2-0.8] are inferred to have precipitated from mixes of end-member hydrothermal fluid and conductively heated seawater. The LREE depletion results from the presence of very stable LREE chloro-complexes that effectively limit the availability of the LREE for partitioning into anhydrite. Above 250°C, Eu is present only in divalent form as chloride complexes, and discrimination against Eu2+ is likely due to both the mismatch in ionic radii between Eu2+ and Ca2+, and the strong chloro-complexation of divalent Eu which promotes stability in the fluid and inhibits partitioning of Eu2+ into precipitating anhydrite. These variations in REE behavior attest to rapid fluctuations in thermal regime, fluid flow and mixing in the subsurface of the TAG mound that give rise to heterogeneity in the formation conditions of individual anhydrite crystals.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

Dissolved Si isotope composition measured in water samples during METEOR cruises M77/3 and M77/4

Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (d30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions d30Si(OH)4 (+2.2 per mil to +4.4 per mil) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 µmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 µmol/kg are characterized by a large range in d30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the d30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean d30Si(OH)4 of +1.2±0.2 per mil, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher d30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between d30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of d30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Physical oceanography and ADCP measurements during POSEIDON cruise P414 (POS414)

Until the eighties the main source of deep water masses in the Ionian Basin was the southern Adriatic Sea. During the nineties a dramatic climatic change took place in the eastern Mediterranean (Eastern Mediterranean Transient); deep water was formed of water originating from the Aegean Sea since then. This change in the deep water had extensive consequences for the whole circulation of the eastern Mediterranean Sea. Expeditions carried out in this region during the last years indicate now that the process of deep water formation might reverse again. The process of this re-reversing deep water formation is a long-term one. Therefore, the characteristics of the today's deep water masses in the Ionian Basin, to which extent these characteristics differ from the deep water masses before the EMT and in which state the re-reversed Eastern Mediterranean deep water circulation is now, must be investigated continuously. The Adriatic deep water finds its way to the Ionian Basin on several routes with different entrainments rates. The entrainment rates might be a deciding factor for the Deep Ionian Waters and the resulting density might influence the role of the Aegean Deep Water for the Ionian Deep Waters as well. Therefore, it is crucial to identify and quantify the routes and entrainment rates of the Adriatic Deep Water. The cruise carried out is a continuation of the work carried out during the cruises POS298, M71/3, MSM13/2, MSM15/4 and M84/3. The objective is to investigate the spatial and temporal variability of dispersion and mixing of the Ionian Deep Water. During the cruise CTD stations were carried out and samples for nutrient, oxygen and oxygen isotopes were taken. Continously measurements were made with the vessel mounted ADCP and thermosalinograph. Additionally, on the cruise students were trained on the use of oceanographic equipment.