Beryllium 7 measured during POLARSTERN cruise ARK-XXII/2

The natural cosmogenic radionuclide 7Be (T1/2 = 53.4 d) is supplied to the surface ocean from the atmosphere and, in the Arctic Ocean, can be used as a tracer of the efficiency with which sea ice intercepts the atmospheric fluxes of chemical species and of the importance of ice as a transport mechanism for particulate matter and chemical species. Analyses of 7Be in samples of surface water, surface sea ice, water beneath the ice, sea ice sediments, and precipitation from the Eurasian Basin of the Arctic Ocean show that the fraction of sea ice coverage determines the amount of 7Be in the surface water. When sea ice coverage is <40%, the 7Be inventory in the upper ocean (130 ± 19 Bq m**-2) is in good agreement with that expected from the inventory from 7Be atmospheric flux (128 ± 21 Bq m**-2). In contrast, when ice coverage is >80%, the water column inventory drops to 58 ± 20 Bq m**-2. The 7Be inventory in sea ice is 39 ± 23 Bq m**-2, and mass balance calculations show that sea ice can intercept 30 ± 18% of the atmospheric flux of 7Be during the studied period. We suggest that other atmospherically transported contaminants should be similarly intercepted. 7Be in the ice also can be used to estimate that the annual transport and release of sediment to the ablation area of the Fram Strait is -500 g m**-2, a value comparable to previously measured fluxes in sediment traps deployed in the area.

Geochemistry of surface sediment cores (Table 4)

The mineralogy and geochemistry of a suite of nine manganese nodules from the South Atlantic have been determined. The Ce/La ratios of the nodules were investigated to see if they could be used as redox indicators to trace the oxygen content of the ambient water mass and the flow path of the Antarctic Bottom Water as has previously been successfully carried out in the Pacific Ocean. The Ce/La ratios of the nodules decrease in the sequence Lazarev Sea, Weddell Sea (10.4 and 9.7)>East Georgia Basin (6.5 and 7.1)>Argentine Basin (5.0), but then increase in the Brazil Basin (6.2) and Angola Basin (9.8 and 15.1). A further decrease was observed in the Cape Basin (7.6). An extremely high Ce/La ratio of 24.4 had already been determined for nodules sampled north of the Nares Abyssal Plain in the western North Atlantic. These data reflect the more complicated pattern of bottom water flow in the South Atlantic than in the South Pacific. The penetration of more oxygenated North Atlantic Deep Water into the South Atlantic accounts for the higher Ce/La ratios in the nodules from the Angola and Brazil basins. Based on this study, the flow path of the Antarctic Bottom Water could only be traced as far north as the Argentine Basin. The unique geochemistry of nodules from the central Angola Basin (high Mn/Fe and Ce/La ratios, high contents of Ni, Cu, Zn and Mo) appears to be a function of the nature of the overlying water mass and of the multiple diagenetic sources of metals to the nodules.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera. New data for Cd/Ca support previous work in defining a contrast between waters shallower and deeper than ~2500 m. Measured element partition coefficients in foraminiferal calcium carbonate relative to sea water (D) have been described by means of a one-box model in which elements are extracted by Rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor (alpha), such that D = (1 - f**alpha)/(l - f), where f is the proportion of Ca remaining after precipitation. A modification to the model recognises differences in element speciation. The model is consistent with differences between D[Sr], D[Ba], and D[Cd] in benthic but not planktonic foraminifera. Depth variations in D for Sr and Ba are consistent with the model, as are differences in depth variation of D[Cd] in calcitic and aragonitic benthic foraminifera. The shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m. Observations of unusually lower DCd for some deep waters, not accompanied by similar [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.

U/Th systematics of authigenic carbonates and d18O records from Hydrate Ridge, off the coast of Oregon, USA

Uranium (U) concentrations and activity ratios (d234U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids ("cold seeps") at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 µg/g) and high 234U values (165-317 per mil) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their 230Th/234U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 µg/g) and a mean d234U ratio of 166 ± 3 per mil. Their U isotopes reflect the d234U ratios of the bottom water being enriched in 234U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding d234U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. 230Th/234U ages of chemoherm carbonates range from 7.3 to 267.6 ka. 230Th/234U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The d18OPDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm d18O values from the marine d18O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.

Radium concentration in water samples from the Northeast Atlantic

We present field measurements of air-sea gas exchange by the radon deficit method that were carried out during JASIN 1978 (NE Atlantic) and FGGE 1979 (Equatorial Atlantic). Both experiments comprised repeated deficit measurements at fixed position over periods of days or longer, using a previously descibed precise and fast-acquiaition, automatic radon measuring system. The deficit time series exhibit variations that only partly reflect the expected changes in gas transfer. By evaluating averages over each time series we deduce the following gas transfer velocities (average wind velocity and water temperature in parentheses): JASIN phase 1: 1.6 ± 0.8 m/d (at ~6 m/s, 13°C) JASIN phase 2: 4.3 ± 1.2 m/d (at ~8 m/s, 13°C) FGGE: 1.2 ± 0.4 m/d (at ~5 m/s, 28°C) 0.9 ± 0.4 m/d (at ~7 m/s, 28°C) 1.5 ± 0.4 m/d (at ~7 m/s, 28°C) The large difference betwen the JASIN phase 2 and FGGE values despite quite similare average wind velocity becomes even larger when the values are, however, fully compatible with the range of gas transfer velocities observed in laboratory experiments and the conclusion is suggested that their difference is caused by the highly different wind variability in JASIN and FGGE. We conclude that in gas exchange parameterization it is not sufficinent to consider wind velocity only. A comparison of our observations with laboratory results outlines the range of variations of air-sea gas transfer velocities with wind velocity and sea state. We also reformulate the radon deficit method, in the light of our observed deficit variations, to account explicitely for non-stationary and horizontal inhomogeneity in previous radon work introduces considerable uncertainty in deduced gas transfere velocity. We furthermore discuss the observational rewuirements that have to be met for an adequate exploitation of the radon deficit method, of which an observation area of minimum horizontal inhomogeneity and monitoring of the remaining inhomogeneities are thought to be the most stringent ones.

Holocene DBD and Ti/LOI timeseries from Lake Hajeren on Svalbard, indicators of past glacier activity

The Arctic is warming faster than anywhere else on Earth. Holocene proxy time-series are increasingly used to put this amplified response in perspective by understanding Arctic climate processes beyond the instrumental period. However, available datasets are scarce, unevenly distributed and often of coarse resolution. Glaciers are sensitive recorders of climate shifts and variations in rock-flour production transfer this signal to the lacustrine sediment archives of downstream lakes. Here, we present the first full Holocene record of continuous glacier variability on Svalbard from glacier-fed Lake Hajeren. This reconstruction is based on an undisturbed lake sediment core that covers the entire Holocene and resolves variability on centennial scales owing to 26 dating points. A toolbox of physical, geochemical (XRF) and magnetic proxies in combination with multivariate statistics has allowed us to fingerprint glacier activity in addition to other processes affecting the sediment record. Evidence from variations in sediment density, validated by changes in Ti concentrations, reveal glaciers remained present in the catchment following deglaciation prior to 11,300 cal BP, culminating in a Holocene maximum between 9.6 and 9.5 ka cal BP. Correspondence with freshwater pulses from Hudson Strait suggests that Early Holocene glacier advances were driven by the melting Laurentide Ice Sheet (LIS). We find that glaciers disappeared from the catchment between 7.4 and 6.7 ka cal BP, following a late Hypsithermal. Glacier reformation around 4250 cal BP marks the onset of the Neoglacial, supporting previous findings. Between 3380 and 3230 cal BP, we find evidence for a previously unreported centennial-scale glacier advance. Both events are concurrent with well-documented episodes of North Atlantic cooling. We argue that this brief forcing created suitable conditions for glaciers to reform in the catchment against a background of gradual orbital cooling. These findings highlight the climate-sensitivity of the small glaciers studied, which rapidly responded to climate shifts. The start of prolonged Neoglacial glacier activity commenced during the Little Ice Age (LIA) around 700 cal BP, in agreement with reported advances from other glaciers on Svalbard. In conclusion, this study proposes a three-stage Holocene climate history of Svalbard, successively driven by LIS meltwater pulses, episodic Atlantic cooling and declining summer insolation.

Seawater carbonate chemistry and Ruditapes decussatus biological processes during experiments, 2011

We investigated the effects of ocean acidification on juvenile clams Ruditapes decussatus (average shell length 10.24 mm) in a controlled CO2 perturbation experiment. The carbonate chemistry of seawater was manipulated by diffusing pure CO2, to attain two reduced pH levels (by -0.4 and -0.7 pH units), which were compared to unmanipulated seawater. After 75 days we found no differences among pH treatments in terms of net calcification, size or weight of the clams. The naturally elevated total alkalinity of local seawater probably contributed to buffer the effects of increased pCO2 and reduced pH. Marine organisms may, therefore, show diverse responses to ocean acidification at local scales, particularly in coastal, estuarine and transitional waters, where the physical-chemical characteristics of seawater are most variable. Mortality was significantly reduced in the acidified treatments. This trend was probably related to the occurrence of spontaneous spawning events in the control and intermediate acidification treatments. Spawning, which was unexpected due to the small size of the clams, was not observed for the pH -0.7 treatment, suggesting that the increased survival under acidified conditions may have been associated with a delay in the reproductive cycle of the clams. Future research about the impacts of ocean acidification on marine biodiversity should be extended to other types of biological and ecological processes, apart from biological calcification.

Benthic foraminiferal response to the emergence of the Isthmus of Panama and coincident paleoceanographic changes

Late Cenozoic benthic foraminiferal faunas from the Caribbean Deep Sea Drilling Project (DSDP) Site 502 (3052 m) and East Pacific DSDP Site 503 (3572 m) were analyzed to interpret bottom-water masses and paleoceanographic changes occurring as the Isthmus of Panama emerged. Major changes during the past 7 Myr occur at 6.7-6.2, 3.4, 2.0, and 1.1 Ma in the Caribbean and 6.7-6.4, 4.0-3.2, 2.1, 1.4, and 0.7 Ma in the Pacific. Prior to 6.7 Ma, benthic foraminiferal faunas at both sites indicate the presence of Antarctic Bottom Water (AABW). After 6.7 Ma benthic foraminiferal faunas indicate a shift to warmer water masses: North Atlantic Deep Water (NADW) in the Caribbean and Pacific Deep Water (PDW) in the Pacific. Flow of NADW may have continued across the rising sill between the Caribbean and Pacific until 5.6 Ma when the Pacific benthic foraminiferal faunas suggest a decrease in bottom-water temperatures. After 5.6 Ma deep-water to intermediate-water flow across the sill appears to have stopped as the bottom-water masses on either side of the sill diverge. The second change recorded by benthic foraminiferal faunas occurs at 3.4 Ma in the Caribbean and 4.0-3.2 Ma in the Pacific. At this time the Caribbean is flooded with cold AABW, which is either gradually warmed or is replaced by Glacial Bottom Water (GBW) at 2.0 Ma and by NADW at 1.1 Ma. These changes are related to global climatic events and to the depth of the sill between the Caribbean and Atlantic rather than the rising Isthmus of Panama. Benthic foraminiferal faunas at East Pacific Site 503 indicate a gradual change from cold PDW to warmer PDW between 4.0 and 3.2 Ma. The PDW is replaced by the warmer, poorly oxygenated PIW at 2.1 Ma. Although the PDW affects the faunas during colder intervals between 1.4 and 0.7 Ma, the PIW remains the principal bottom-water mass in the Guatemala Basin of the East Pacific.