(Table S1, S4) Campanian-Maastrichtian benthic foraminifera from ODP Hole 113-690C

During the latest Cretaceous cooling phase, a positive shift in benthic foraminiferal d18O values lasting about 1.5 Myr (71.5-70 Ma) can be observed at a global scale (Campanian-Maastrichtian Boundary Event, CMBE). This d18O excursion is interpreted as being influenced by a change in intermediate- to deep-water circulation or by temporal build-up of Antarctic ice sheets. Here we test whether benthic foraminiferal assemblages from a southern high-latitudinal site near Antarctica (ODP Site 690) are influenced by the CMBE. If the d18O transition reflects a change in intermediate- to deep-water circulation from low-latitude to high-latitude water masses, then this change would result in cooler temperatures, higher oxygen concentration, and possibly lower organic-matter flux at the seafloor, resulting in a major benthic foraminiferal assemblage change. If, however, the d18O transition was mainly triggered by ice formation, no considerable compositional difference in benthic foraminiferal assemblages would be expected. Our data show a separation of the studied succession into two parts with distinctly different benthic foraminiferal assemblages. Species dominating the older part (73.0-70.5 Ma) tolerate less bottom water oxygenation and are typical components of low-latitude assemblages. In contrast, the younger part (70.0-68.0 Ma) is characterized by species that indicate well-oxygenated bottom waters and species common in high-latitude assemblages. We interpret the observed change in benthic foraminiferal assemblages toward a well-oxygenated environment to reflect the onset of a shift from low-latitude toward high-latitude dominated intermediate- to deep-water sources. This implies that a change in oceanic circulation was at least a major component of the CMBE.

Stable oxygen and carbon isotope data for planktic and benthic foraminifera from southern Atlantic of DSDP Hole 74-525A and ODP Hole 113-690C

Published stable isotope records in marine carbonate are characterized by a positive d18O excursion associated with a negative d13C shift during the early Maastrichtian. However, the cause and even the precise timing of these excursions remain uncertain. We have generated high-resolution foraminiferal stable isotope and gray-scale records for the latest Campanian to early Maastrichtian (73-68 Ma) at two Ocean Drilling Program sites, 525 (Walvis Ridge) and 690 (Weddell Sea). We demonstrate that the negative d13C excursion is decoupled from the d18O increase with a lag of about 600 ka. Our d13C records (both planktic and benthic) show an amplitude for the negative excursion of 0.7 per mill that falls between about 72.1 and 70.7 Ma. Our planktic d18O records indicate an overall increase of 1.2 per mill from 73 to 68 Ma at Site 690, whereas at Site 525 they record a slightly smaller increase (1 per mill) that peaks around 70.1 Ma with decreasing values thereafter. Our benthic d18O data indicate an increase of 1.5 per mill at Site 525 and 0.7 per mill at Site 690 between about 71.4 and 69.9 Ma. Benthic d18O values show different baseline values at the two sites before and after the excursion, but the larger increase at Site 525 means that the values attained at the peak of the excursion are similar at the two sites. We interpret this observation in terms of water mass changes. The excursion is interpreted to reflect a cooling of bottom waters in response to the strengthening contribution of intermediate- to deep-water production in the high southern latitudes rather than increased ice volume. The associated carbon cycle perturbations that we observe are interpreted to reflect a weakening of surface water stratification and increased productivity, as supported by our gray value data.

(Fig. 1) Stable carbon and oxygen isotope ratios of foraminifera of ODP Hole 113-690B

A remarkable oxygen and carbon isotope excursion occurred in Antarctic waters near the end of the Palaeocene (~57.33 Myr ago), indicating rapid global warming and oceanographic changes that caused one of the largest deep-sea benthic extinctions of the past 90 million years. In contrast, the oceanic plankton were largely unaffected, implying a decoupling of the deep and shallow ecosystems. The data suggest that for a few thousand years, ocean circulation underwent fundamental changes producing a transient state that, although brief, had long-term effects on environmental and biotic evolution.

Paleomagnetic age assigments of ODP Site 113-697 (Table 1)

At Site 697 a 320 m thick Pleistocene and Pliocene section was recovered, consisting of hemipelagic terrigenous mud with varying amounts of diatoms, thin altered ash layers, and ice-rafted debris (IRD). Sedimentation rates range from 41 m/m.y. (upper Pleistocene) to 150 m/m.y. (lower Pliocene). Diatom percentage and sediment grain-size have been measured for the whole section with approximately one sample per 5,000 yr. IRD is most abundant in the lower Pliocene (sediments older than 4.5 Ma) following the first major West Antarctic glaciation. A decrease in IRD to near-zero above 3.2 Ma may record a transition from valley glaciers to a grounded ice-sheet on West Antarctica. Bottom current flow, recorded in sediments as the proportion of silt, was at a maximum around 3.0-3.3 Ma then gradually decreased until 0.5 Ma. In the upper Pleistocene, maxima in diatom percentage are assumed to occur during interglacials, implying reduced sea-ice cover; maxima in silt percentage correspond to diatom maxima, implying stronger bottom water flow during interglacials.

Benthic foraminifera and phytodetritus species in sediments from DSDP Leg 85, and ODP Legs 113 and 143

From late middle Eocene through earliest Oligocene, high-latitude regions cooled, and by the end of the period, continental ice sheets existed in Antarctica. Diversity of planktonic microorganisms declined, and modern groups of terrestrial vertebrates originated. Coeval faunal changes in deep-sea benthic foraminifers have been related to cooling of deep waters and increased oxygenation. Cooling, however, occurred globally, whereas species richness declined at high latitudes and not in the tropics. The late Eocene and younger lower-diversity, high-latitude faunas typically contain common Epistominella exigua and Alabaminella weddellensis, opportunistic phytodetritus-exploiting species that indicate a seasonally fluctuating input of organic matter to the sea floor. We speculate that the species-richness gradient and increase in abundance of phytodetritus-exploiting species resulted largely from the onset of a more unpredictable and seasonally fluctuating food supply, especially at high latitudes.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

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).

Stable carbon and oxygen isotope ratios of calcareous dinoflagellate cysts and planktic foraminifera from the Campanian/Maastrichtian section of ODP Hole 113-690C in the Weddell Sea (Table 1)

Delta18O and delta13C values for the calcareous dinoflagellate species Orthopithonella? globosa (Fütterer 1984) Lentin and Williams 1985 and Pirumella krasheninnikovii (Bolli 1974) Lentin and Williams 1993 from lates Campanian and earliest Maastrichtian of ODP Hole 690C (Weddell Sea, Antarctic Ocean) have been studied in order to evaluate the species' depth habitat in the water column and their applicability in paleoceanographic studies. The calcareous dinoflagellates show isotopic values comparable to probably shallow-dwelling planktic foraminifera from the same sample in delta18O, but have an offset of about -5 ? to -7? in delta13C. This suggests that calcareous dinoflagellate oxygen isotopes may provide information for paleoceanographic reconstructions of sea-surface water temperatures, whereas their extremely light carbon isotope values are probably due to photosynthetic processes.