TOC, CaCO3, n-alkane and alkenone concentrations of ODP Sites 202-1237 and 202-1239

We generated preliminary downcore records of total organic carbon content, calcium carbonate, long-chain n-alkane concentration, total alkenone concentration, and alkenone-based sea-surface temperature for samples from the easternmost flank of Nazca Ridge (Site 1237) and the eastern crest of Carnegie Ridge (Site 1239). Total organic carbon and long-chain n-alkane concentrations will be used to evaluate terrestrial sediment sources. Downcore records of alkenone sea-surface temperature will benefit studies of paleoceanography of the southeastern Pacific. Since these sites are located under the influence of major tectonic events, such as the uplift of the Andes Mountains and the closure of the Isthmus of Panama, the records will help us to examine the effects of the tectonic events on the oceanic environment.

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Isotope and Mg/Ca measurements from Cores ME0005A-43JC and 202-1242 of tropical Pacific

Multiproxy geologic records of d18O and Mg/Ca in fossil foraminifera from sediments under the Eastern Pacific Warm Pool (EPWP) region west of Central America document variations in upper ocean temperature, pycnocline strength, and salinity (i.e., net precipitation) over the past 30 kyr. Although evident in the paleotemperature record, there is no glacial-interglacial difference in paleosalinity, suggesting that tropical hydrologic changes do not respond passively to high-latitude ice sheets and oceans. Millennial variations in paleosalinity with amplitudes as high as 4 practical salinity units occur with a dominant period of 3-5 ky during the glacial/deglacial interval and 1.0-1.5 ky during the Holocene. The amplitude of the EPWP paleosalinity changes greatly exceeds that of published Caribbean and western tropical Pacific paleosalinity records. EPWP paleosalinity changes correspond to millennial-scale climate changes in the surface and deep Atlantic and the high northern latitudes, with generally higher (lower) paleosalinity during cold (warm) events. In addition to Intertropical Convergence Zone (ITCZ) dynamics, which play an important role in tropical hydrologic variability, changes in Atlantic-Pacific moisture transport, which is closely linked to ITCZ dynamics, may also contribute to hydrologic variations in the EPWP. Calculations of interbasin salinity average and interbasin salinity contrast between the EPWP and the Caribbean help differentiate long-term changes in mean ITCZ position and Atlantic-Pacific moisture transport, respectively.

Stable carbon and oxygen isotopes and Mg/Ca ratios of foraminifers from ODP Site 202-1241 sediments

A combination of stable isotope records and Mg/Ca temperature estimates of four different planktonic foraminiferal species from Ocean Drilling Program Site 1241 allows differentiation between temperature and salinity changes in the tropical east Pacific (TEP) upper water column during the Pliocene (~5.7-2.1 Ma). The deviation of d18O records and Mg/Ca temperature estimates from thermocline-dwelling planktonic foraminifers suggests that local changes in salinity exerted a much stronger control on Pliocene TEP upper ocean water mass signatures than previously assumed. The most pronounced Pliocene change in TEP upper ocean stratification was the shoaling of the thermocline from ~4.8 to 4.0 Ma that was possibly triggered by changes in the configuration of low-latitude ocean gateways. During this time interval, mixed-layer temperatures and salinities remained relatively constant in contrast to a pronounced temperature (~6°C) and salinity decrease at the bottom of the photic zone. This change led to a new state in the thermal structure of the TEP, as the thermocline remained relatively shallow until ~2.1 Ma.

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).

(Appendix A) Radiolarian abundance in ODP Hole 202-1241A

A quantitative radiolarian study at Ocean Drilling Program Site 1241 in the eastern tropical Pacific enables us to reconstruct paleoceanographic changes that occurred since the latest middle Miocene. Today, this site is located just under the Eastern Pacific Warm Pool (EPWP). Based on the abundance variations of radiolarian characteristic species which are indicators of upwelling and thermocline changes, it is suggested that three notable changes occurred at 10.6, 9.8, and 4.2 Ma in the region. Four distinct periods of oceanographic conditions bounded by these notable changes were characterized on the basis of the following: (1) stratified seawater (12.0 to 10.6 Ma); (2) a shallowing of the thermocline and an increasing of upwelling (10.6 to 9.8 Ma); (3) significant inflow of warm water to the eastern tropical Pacific caused by an intensified Northern Equatorial Countercurrent (NECC), resulting in the formation of EPWP (9.8 to 4.2 Ma); and (4) the reduction of the EPWP and the NECC, and an increase in upwelling (4.2 to 0 Ma). The timing of these paleoceanographic events indicated the strong relations with the opening and closing of the Indonesian and Central American (Panama) Seaways. The reduction of the EPWP (this study) and the deepening of the thermocline in western Pacific at about 4.2 Ma (Cannariato and Ravelo, 1997; Chaisson and Ravelo, 2000) indicated a change from a state resembling El Niño in the late Miocene and the early Pliocene time to a state resembling La Niña by the late Pliocene