(Appendix 1) Crustal helium-4 abundance and flux data for ODP Hole 130-806B

The mass accumulation rates (MARs) of aeolian dust in the ocean basins provide an important record of climate in the continental source regions of atmospheric dust and of the prevailing wind patterns responsible for dust transport in the geologic past. The incorporation of other terrigenous components such as volcanic ashes in seafloor sediments, however, often obscures the aeolian dust record. We describe a new approach which uses the delivery rate of crustal 4He to seafloor sediments as a proxy for the mass accumulation rate of old continental dust which is unaffected by the addition of other terrigenous components. We have determined the flux of crustal 4He delivered to the seafloor of the Ontong Java Plateau (OJP) in the western equatorial Pacific over the last 1.9 Myrs. Crustal 4He fluxes vary between 7.7 and 30 ncc/cm**2/kyr and show excellent correlation with global climate as recorded by oxygen isotopes, with high crustal 4He fluxes associated with glacial periods over the entire interval studied. Furthermore, the onset of strong 100 kyr glacial-interglacial climate cycling is clearly seen in the 4He flux record about 700 kyrs ago. These data record variations in the supply of Asian dust in response to climate driven changes in the aridity of the Asian dust sources, consistent with earlier work on Asian dust flux to the northern Pacific Ocean. However, in contrast to previous studies of sites in the central and eastern equatorial Pacific Ocean, there is no evidence that the Inter Tropical Convergence Zone (an effective rainfall barrier to the southward transport of northern hemisphere dust across the equator in the central and eastern Pacific) has influenced the delivery of Asian dust to the OJP. The most likely carrier phase for crustal helium in these sediments is zircon, which can reasonably account for all the 4He observed in the samples. As a first order estimate, these results suggest that the mass accumulation rate of Asian dust on the OJP over the last 1.9 Myrs varied from about 4 to 15 mg/ cm**2/kyr. In contrast, previous studies show that over the same interval the total MAR of terrigenous dust (i.e. Asian dust plus local volcanics) on OJP varied between about 34 and 90 mg/ cm**2/kyr.

Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Greenland and Antarctic ice sheet topography, cavity geometry, and global bathymetry (RTopo-2), links to NetCDF files

The ocean plays an important role in modulating the mass balance of the polar ice sheets by interacting with the ice shelves in Antarctica and with the marine-terminating outlet glaciers in Greenland. Given that the flux of warm water onto the continental shelf and into the sub-ice cavities is steered by complex bathymetry, a detailed topography data set is an essential ingredient for models that address ice-ocean interaction. We followed the spirit of the global RTopo-1 data set and compiled consistent maps of global ocean bathymetry, upper and lower ice surface topographies and global surface height on a spherical grid with now 30-arc seconds resolution. We used the General Bathymetric Chart of the Oceans (GEBCO, 2014) as the backbone and added the International Bathymetric Chart of the Arctic Ocean version 3 (IBCAOv3) and the Interna- tional Bathymetric Chart of the Southern Ocean (IBCSO) version 1. While RTopo-1 primarily aimed at a good and consistent representation of the Antarctic ice sheet, ice shelves and sub-ice cavities, RTopo-2 now also contains ice topographies of the Greenland ice sheet and outlet glaciers. In particular, we aimed at a good representation of the fjord and shelf bathymetry sur- rounding the Greenland continent. We corrected data from earlier gridded products in the areas of Petermann Glacier, Hagen Bræ and Sermilik Fjord assuming that sub-ice and fjord bathymetries roughly follow plausible Last Glacial Maximum ice flow patterns. For the continental shelf off northeast Greenland and the floating ice tongue of Nioghalvfjerdsfjorden Glacier at about 79°N, we incorporated a high-resolution digital bathymetry model considering original multibeam survey data for the region. Radar data for surface topographies of the floating ice tongues of Nioghalvfjerdsfjorden Glacier and Zachariæ Isstrøm have been obtained from the data centers of Technical University of Denmark (DTU), Operation Icebridge (NASA/NSF) and Alfred Wegener Institute (AWI). For the Antarctic ice sheet/ice shelves, RTopo-2 largely relies on the Bedmap-2 product but applies corrections for the geometry of Getz, Abbot and Fimbul ice shelf cavities.

Magnesium/Calcium ratios in benthic foraminifera from surface sediments

We used modern epibenthic foraminifer tests of Cibicidoides mundulus and Planulina wuellerstorfi from South Atlantic core top sediments in order to establish Mg/Ca-temperature relationships for the temperature range from 0 to 15°C. We obtained the following calibrations: Mg/Ca (mmol/mol) = 0.830*exp(0.145*BWT (°C)) for P. wuellerstorfi, and Mg/Ca (mmol/mol) = 0.627*exp(0.143*BWT (°C)) for C. mundulus. However, a number of tests, especially those bathed in North Atlantic Deep Water, revealed higher Mg/Ca ratios than predicted from the calibration. Our data suggest that d[CO3 2-] of bottom water exerts a significant control on dMg/Ca (temperature-corrected) of C. mundulus (dMg/Ca = 0.017*d[CO3 2-] -0.14), while dMg/Ca of P. wuellerstorfi is more likely to be governed by TCO2 (dMg/Ca = -0.007*TCO2 + 15). Since both d[CO3 2-] and TCO2 are closely linked to [CO3 2-], it is inferred that carbonate ion acts as secondary control, after temperature, on benthic shell Mg/Ca below -4°C. A drop in [CO3 2-] by 25 ?mol/kg at 4 km water depth, as suggested for the Last Glacial Maximum, would decrease Mg/Ca by up to 0.4 mmol/mol, which leads to an underestimation of bottom water temperature by -3.5°C. Therefore our results indicate that the Mg/Ca thermometer should be used cautiously for benthic foraminifers where changes in the carbonate chemistry are present in the paleoceanographic record.

Methane and sulphate consumption in different habitats of the Håkon Mosby Mud Volcano (HMMV)

The Hakon Mosby Mud Volcano is a highly active methane seep hosting different chemosynthetic communities such as thiotrophic bacterial mats and siboglinid tubeworm assemblages. This study focuses on in situ measurements of methane fluxes to and from these different habitats, in comparison to benthic methane and oxygen consumption rates. By quantifying in situ oxygen, methane, and sulfide fluxes in different habitats, a spatial budget covering areas of 10-1000 -m diameter was established. The range of dissolved methane efflux (770-2 mmol m-2 d-1) from the center to the outer rim was associated with a decrease in temperature gradients from 46°C to < 1°C m-1, indicating that spatial variations in fluid flow control the distribution of benthic habitats and activities. Accordingly, total oxygen uptake (TOU) varied between the different habitats by one order of magnitude from 15 mmol m-2 d-1 to 161 mmol m-2 d-1. High fluid flow rates appeared to suppress benthic activities by limiting the availability of electron acceptors. Accordingly, the highest TOU was associated with the lowest fluid flow and methane efflux. This was most likely due to the aerobic oxidation of methane, which may be more relevant as a sink for methane as previously considered in submarine ecosystems.

Table 2. Lead and Ba concentrations and Pb isotopic compositions measured in Law Dome ice cores

Lead isotopic compositions and Pb and Ba concentrations have been measured in ice cores from Law Dome, East Antarctica, covering the past 6500 years. 'Natural' background concentrations of Pb (ab. 0.4 pg/g) and Ba (ab. 1.3 pg/g) are observed until 1884 AD, after which increased Pb concentrations and lowered 206Pb/207Pb ratios indicate the influence of anthropogenic Pb. The isotopic composition of 'natural' Pb varies within the range 206Pb/207Pb=1.20-1.25 and 208Pb/207Pb=2.46-2.50, with an average rock and soil dust Pb contribution of 8-12%. A major pollution event is observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration four-fold and changing 206Pb/207Pb ratios in the ice to ab. 1.12. Based on Pb isotopic systematics and Pb emission statistics, this is attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia. Anthropogenic Pb inputs are at their greatest from 1900 to 1910 and from ab. 1960 to ab. 1980. During the 20th century, Ba concentrations are consistently higher than 'natural' levels and are attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation.

Foraminifera Mg/Ca, test weight and XDX for sediment core WIND28K

A record of deep-sea calcite saturation (D[CO3**-2]), derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (~15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ~4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ~4°C colder in MIS 3 compared to the Holocene (8 ka B.P.).

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).