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).

Organic carbon, freely extractable lipids and ketone recovery of ODP Leg 199 sediments

Six samples from Sites 1219 and 1221 ranging in age from early Eocene to early Oligocene were analyzed for freely extractable lipids to determine whether the low organic carbon (Corg) sediments of the Eocene equatorial Pacific (Corg content typically 0.03%) are appropriate for biomarker studies. Only one sample from the Oligocene equatorial Pacific (Sample 199-1219A-13H-3, 50-54 cm) contained any biomarkers of interest to paleoceanography. The only lipids identified in the remaining samples appear to be contaminants from drilling or subsequent handling. Sample 199-1219A-13H-3, 50-54 cm, contained alkenone biomarkers specific to haptophyte algae that are used for estimating past mean annual sea-surface temperature (maSST). If the Holocene calibration of maSST is appropriate for the Oligocene, the estimated equatorial temperature is >=28.3°C, or at least 3°C warmer than modern equatorial maSST at a similar longitude.

(Table 1) Planktonic foraminifer abundance and stable isotope ratios of a sediment core near Baddeckenstedt, north Germany

A refined sample processing technique using glacial acetic acid has been applied to Upper Cenomanian and Lower Turonian limestones from Baddeckenstedt (Lower Saxony) enabeling the first quantitative analysis of planktonic foraminiferal populations through the Stage boundary succession in northwestern Germany. Measurements of carbonate contents, organic carbon and stable carbon and oxygen isotopes were also reported. These data allow a correlation to be made of the Baddeckenstedt section with those at Misburg (basinal facies, northwestern Germany) and Dover (Plenus Marls, southern England). Significant maxima of the organic carbon content at Baddeckenstedt correspond to prominent black shale couplets at Misburg. The planktonic foraminiferal generic groups show at Baddeckenstedt similar fluctuations as reported from Dover. Their correlation reveals details of a complex paleoceanographic regime in the NW-German Basin during the Cenomanian/Turonian Oceanic Anoxic Event.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Composition and origin of sediments at DSDP Site 54-424

The sediments recovered on Deep Sea Drilling Project Leg 54 appear to be mixtures of the normal pelagic sediments of the area and hydrothermally produced manganese and iron phases. The latter are mineralogically and chemically very similar to phases recovered from surficial sampling of the mounds. The hydrothermal nontronite which is approximately 15 meters thick in the three holes is essentially free of carbonate or detrital contaminants. The basal sediments are similar to the carbonate oozes presently being deposited in the region, but are enriched in Mn and Fe. This enrichment appears to be the result of hydrothermal deposition that took place at or near the spreading center and may not be associated with the mounds formation. Three different hypotheses for the formation of the nontronite layer and the mounds deposits are considered. An initial deposition of a widespread nontronite layer and subsequent diapiric-like movement of the layer into carbonates could account for the observed stratigraphy; however, if this be correct, analogous deposits should be present in other DSDP sites. The second hypothesis - replacement of the normal sediments by nontronite - may be feasible, but the high purity of the nontronite requires dissolution and removal of refractory elements. The third hypothesis, metal deposition in an advancing oxidation gradient, is compatible with submersible observations of the mounds; however, it can account only for the high purity of the nontronite by very rapid deposition of the hydrothermal phases.

Geochemistry of ODP Sites 121-758 and 121-757

Nd isotopes are useful tracers for paleoceanography due to the short Nd residence time in seawater and the large differences between the isotopic signatures of various geological reservoirs. Therefore, ?Nd variations reflect the geological history of individual oceanic basins. Using a differential dissolution technique, which extracts Nd isotopes of seawater trapped in MnO2 coatings and carbonates in marine sediment, we measured almost two hundred samples from ODP Sites 758 and 757 in the Northern Bay of Bengal covering the last 4 Ma. For the first time, we have shown a covariation between epsilon-Nd and d18O over at least the last 800 ka. We also show that from 4 Ma to 2.6 Ma, epsilon-Nd is almost constant and starts to fluctuate at 2.6 Ma when northern glaciations increased. From 2.6 Ma to 1 Ma the fluctuation period is close to 40 ka while from 1 Ma to present it is dominantly 100 ka. We attribute these findings to mixing between Himalayan river water (that ultimately originates as Indian summer monsoon rain) and normal Bay of Bengal seawater. Previous studies on seawater, using epsilon-Nd, d18O analyzed on planktonic foraminifera and sedimentary data, can be integrated into this model. A simple quantitative binary mixing model suggests that the summer monsoon rain was more intense during interglacial than glacial periods. During last glacial episode, the monsoon trajectory was deviated to the east. At a large scale, the Indian monsoon is fully controlled by the variations in Northern Hemisphere climate but with a complex response function to this forcing. Our study clearly establishes the large potential of Nd isotope data to evaluate the hydrological river regime during the Quaternary and its relationship with climate fluctuations, particularly when the sediment archive is sampled close to sediment sources.

Composition of sediments from the north-west African continental margin

Entlang dreier Profile vom NW-afrikanischen Kontinentalrand wurden Oberflächensedimente aus Wassertiefen zwischen 39m und 1514m auf ihre Zusammensetzung der Sandfraktion, auf ihre Gehalte an Karbonat und organischer Substanzen sowie auf ihre mineralogische Zusammensetzung hin untersucht. 1) Die auf dem Schelf und dem oberen Hang abgelagerten Sedimente (<500m) zeichnen sich durch hohe Sandgehalte (>70%) und durch hohe Grob/Fein-Verhältnisse aus. Unterhalb dieses Bereiches nimmt der Einfluß von Strömungen, die die Ablagerung von wesentlichen Mengen an Feinmaterial oberhalb 500m verhindern, ab, wie die starke Abnahme des Sandgehaltes, des Quarz/Glimmer und des Grob/Fein-Verhältnisses zeigen. Die Sedimente aus diesen Wassertiefen werden zum großen Teil aus Partikeln der Siltfraktion aufgebaut. Mit zunehmender Tiefe ist auch eine Zunahme der Tonfraktion zu beobachten, wobei höhere Tonanteile (>10%) erst in Tiefen unterhalb von 1200m auftreten. 2) Die quantitative Komponentenanalyse der Sandfraktion zeigt, daß der karbonatische Anteil fast ausschließlich biogener Herkunft ist. Er besteht zum wesentlichen Teil aus planktonischen Komponenten, vorwiegend Foraminiferen und mengenmäßig nur sehr untergeordnet auftretenden Pteropoden. Das opalkieselige Plankton (Diatomeen, Radiolarien) ist nur in geringen Mengen in den untersuchten Proben vorhanden. Auch das Benthos stellt nur eine untergeordnete Komponente der Sandfraktion dar. Vor allem der Anteil von Foraminiferen und Mollusken nimmt mit zunehmender Wassertiefe relativ deutlich ab. Die übrigen benthonischen Komponenten sind im Sediment nur in geringen Anteilen vertreten. 3) Hauptsedimentbildner im Profil Nouakchott sind die nichtbiogenen, terrigen-detritischen Sandkomponenten. Sie bestehen vorwiegend aus Quarz und mit zunehmender Wassertiefe aus Kotpillen bzw. Kotpillenaggregaten. Je nach Tiefe treten vor allem Glimmer (>1000m) und Glaukonit (<800m) hinzu. Die restlichen Komponenten treten nur gelegentlich und in äußerst geringen Mengen im rezenten Oberflächensediment auf. 4) Quarz wird als Windstaub mit dem NE-Passat und vor allem durch den "Harmattan" aus der Sahara heraustransportiert und vorwiegend über dem Schelfbereich sedimentiert. Windstaubmaterial besteht primär weitgehend aus Siltkorngrößen, die vor Nouakchott über die Schelfkante hinaustransportiert werden und zu einer Grobsiltanreicherung am mittleren Hang führen. 5) Das Verhältnis zwischen den karbonatischen Biogenkomponenten und den nichtbiogenen Partikeln spiegelt sich deutlich in der Karbonatverteilung sowohl des Gesamtsedimentes als auch der Sandfraktion wider. Relativ hohe Karbonatgehalte vor Cap Leven im Norden stehen sehr geringen Anteilen von Nouakchott gegenüber. Mit zunehmender Wassertiefe ist eine deutliche Abnahme des Karbonatanteils zu verfolgen. 6) Die Tatsache, daß das Profil Cap Blanc im Bereich des ganzjährigen Auftriebs liegt, spiegelt sich nicht in der Zusammensetzung der Sandfraktion wider. Südlich der Zone des ganzjährigen Auftriebs weisen verschiedene Parameter (Radiolarien, Diatomeen, Verhältnis von Radiolarien zu planktonischen Foraminiferen, Benthos/Plankton-Verhältnis der Foraminiferen) trotz abnehmender Auftriebsintensität eher steigende Werte auf. Dies ist wesentlich auf eine infolge des Nährstoffeintrages durch Flußzufuhr bedingte Verschiebung der maximalen Primärproduktion weit in südliche Richtung zurückzuführen. 7) In den aufgeführten Parametern zeigen sich von Profil zu Profil sehr deutliche fazielle Unterschiede, obwohl der großklimatische Hintergrund im gesamten Untersuchungsgebiet etwa gleich ist. Vor Cap Leven bildet sich eine Fazies, die im wesentlichen aus planktonischen Foraminiferen besteht, während das Sediment vor Nouakchott zum überwiegenden Teil aus nichtbiogenen Komponenten aufgebaut wird. Im Übergangsbereich vor Cap Blanc bildet sich eine Mischfazies, die keinerlei Prägung durch das Auftriebsgeschehen erhält. Die Ursachen dieser faziellen Unterschiede werden auf fehlenden Terrigeneinfluß vor Cap Leven einerseits und hohe Terrigenanlieferung vor Nouakchott andererseits zurückgeführt. 8) Die Zusammensetzung und Verteilung der rezenten Grobfraktionssedimente am Kontinentalrand vor Nw-Afrika wird somit im wesentlichen als Ergebnis einer Überprägung der Biogenanlieferung durch nichtbiogene Komponenten angesehen. Wesentlicher steuernder Faktor ist demnach das hier vorherrschende Windsystem.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.