Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

(Table 1) Presence of sublittoral macroalgae in the investigated profiles in Potter Cove, King George Island, Antarctica

The vegetation of a small fjord and its adjacent open shore was documented by subaquatic video. The distribution of individual species of macroalgae and the composition of assemblages were compared with gradients of light availability, hydrography, slope inclination, substratum, and exposition to turbulence and ice. The sublittoral fringe is usually abraded by winterly ice floes and devoid of large, perennial algae. Below this zone, the upper sublittoral is dominated by Desmarestia menziesii on steep rock faces, where water movements become irregular, or by Ascoseira mirabilis and Palmaria decipiens on weakly inclined slopes with steady rolling water movements. In the central sublittoral above 15 m, where turbulence is still active, Desmarestia anceps is outcompeting all other species on solid substratum, However, the species is not able to persist on loose material under these conditions. Instead, Himantothallus grandifolius may occur. Deeper, where turbulence usually is negligible, Desmarestia anceps also covers loose material. The change of dominance to Himantothallus grandifolius in the deep sublittoral cannot completely be explained at present. Himantothallus grandifolius also prevails in a mixed assemblage under the influence of grounding icebergs. Most of the smaller algae are opportunists with different degrees of tolerance for turbulence, but some apparently need more stable microhabitats and thus are dependent from continuing suppression of competitive large phaeophytes.

(Table 1) Abundance of radiolarians in the surface layer of bottom sediments from the Peru-Chile trench and shelf

Two radiolarian assemblages are distinguished: an equatorial sub-assemblage of the tropical assemblage in the East Pacific Ocean, which differs somewhat from association of radiolarians in the western part of the ocean, and an assemblage close to transitional one between the tropical and the boreal. The latter is characterized by presence of considerable number of species typical for cold-water regions. Some criteria are presented for distinguishing radiolarian associations in nearshore regions from similar associations in regions of the open ocean.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

(Table 3) Concentrations of polybrominated diphenyl ether and congeners in blubber samples from whales, seals and porpoises between 1986-2009

A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments.

(Table 2) Rates of nitrate and ammonium uptake, concentrations of particulate organic nitrogen and carbon, and dissolved nitrate and ammonium in waters of the Black Sea August-September 1990 and November 1991

To study inorganic nitrogen uptake rates by microplankton in the Black Sea the first 15N-experiments were carried out in August-September 1990 and in November 1991. In surface waters nitrate uptake rates varied from 5.7 to 28.5 nM/l/h in summer and from 1.9 to 7.8 nM/l/h in autumn. In both seasons maximal and minimal rates were observed in frontal zones of shelf/slope areas and in open waters, respectively. In summer average nitrate uptake rate per unit of particulate organic nitrogen was 0.0037 1/h for all stations. In autumn it varied from 0.0007 1/h in the central part of the sea to 0.0033 1/h in the slope near the southeastern Crimean coast. In autumn ammonium uptake rate varied from 7.1 to 22.2 nM/l/h and from 0.0025 to 0.00094 1/h. Ammonium uptake correlated linearly with nitrate uptake, with new production being 22-36% of total summary nitrate and ammonium uptake. There was a linear correlation between nitrogen uptake and chlorophyll a concentrations in the Black Sea. In the water column in autumn both nitrate and ammonium uptake decreased as chlorophyll a concentration diminishes with depth.

(Table 1) Beluga (Delphinapterus leucas) density and abundance, and pod characteristics in west Greenland waters

An aerial survey was conducted to estimate the abundance of belugas (Delphinapterus leucas) on their wintering ground in West Greenland in March-April 2006 and 2008. The survey was conducted as a double platform aerial line transect survey, and sampled approximately 17% of the total survey area of ca. 125 000 km**2. The abundance of belugas was 10 595 (95% confidence interval 4904-24 650). The largest abundance was found at the northern part of Store Hellefiske Bank, at the eastern edge of the Baffin Bay pack ice, a pattern similar to that found in eight systematic surveys conducted since 1981. A clear relationship between decreasing sea-ice cover and increasing offshore distance of beluga sightings was established from all previous surveys, suggesting that belugas expand their distribution westward as new areas on the banks of West Greenland open up earlier in spring with reduced sea-ice coverage or early annual ice recession. This is in contrast to the relatively confined distribution of belugas near the coast in limited open areas in the early 1980s, when sea-ice cover was greater. However, the effects of the changes in coastal availability of belugas can also be observed with the correlation between catches from the local Inuit hunt and sea-ice cover, where the catches increased significantly with increasing sea-ice coverage during the period 1954-2006. These results, based on nearly 30 years of dedicated survey effort, are among the first available evidence showing a shift in distribution of an Arctic cetacean in response to changes in sea-ice coverage.

Relative abundance of pteropod species of the plankton pump samples in the surface water of the eastern North Atlantic Ocean (Table 4)

Plankton pump samples and plankton tows (size fractions between 0.04 mm and 1.01 mm) from the eastern North Atlantic Ocean contain the following shell- and skeleton-producing planktonic and nektonic organisms, which can be fossilized in the sediments: diatoms, radiolarians, foraminifers, pteropods, heteropods, larvae of benthic gastropods and bivalves, ostracods, and fish. The abundance of these components has been mapped quantitatively in the eastern North Atlantic surface waters in October - December 1971. More ash (after ignition of the organic matter, consisting mostly of these components) per cubic meter of water is found close to land masses (continents and islands) and above shallow submarine elevations than in the open ocean. Preferred biotops of planktonic diatoms in the region described are temperate shallow water and tropical coastal upwelling areas. Radiolarians rarely occur close to the continent, but are abundant in pelagic warm water masses, even near islands. Foraminifers are similar to the radiolarians, rarer in the coastal water mass of the continent than in the open ocean or off oceanic islands. Their abundance is highest outside the upwelling area off NW Africa. Molluscs generally outnumber planktonic foraminifers, implying that the carbonate cycle of the ocean might be influenced considerably by these animals. The molluscs include heteropods, pteropods, and larvae of benthic bivalves and gastropods. Larvae of benthic molluscs occur more frequently close to continental and island margins and above submarine shoals (in this case mostly guyots) than in the open ocean. Their size increases, but they decrease in number with increasing distance from their area of origin. Ostracods and fish have only been found in small numbers concentrated off NW Africa. All of the above-mentioned components occur in higher abundances in the surface water than in subsurface waters. They are closely related to the hydrography of the sampled water masses (here defined through temperature measurements). Relatively warm water masses of the southeastern branches of the Gulf Stream system transport subtropical and southern temperate species to the Bay of Biscay, relatively cool water masses of the Portugal and Canary Currents carry transitional faunal elements along the NW African coast southwards to tropical regions. These mix in the northwest African upwelling area with tropical faunal elements which are generally assumed to live in the subsurface water masses and which probably have been transported northwards to this area by a subsurface counter current. The faunas typical for tropical surface water masses are not only reduced due to the tongue of cool water extending southwards along the coast, but they are also removed from the coastal zone by the upwelling subsurface water masses carrying their own shell and skeleton assemblages. Tropical water masses contain much more shelland skeleton-producing plankters than subtropical and temperate ones. The climatic conditions found at different latitudes control the development and intensity of a separate continental coastal water mass with its own plankton assemblages. Extent of this water mass and steepness of gradients between the pelagic and coastal environment limit the occurrence of pelagic plankton close to the continental coast. A similar water mass in only weakly developed off oceanic islands.

(Table 1) Primary production and chlorophyll a concentration in the Northeastern Tropical Atlantic

Results of simultaneous determinations of chlorophyll "a" concentrations and primary production in the northeastern part of the Tropical Atlantic in spring 1977 are discussed. Primary production was low (250-350 mg C/m**2/day in the open parts of the ocean and high (600-1500 mg C/m**2/day) mainly in zones of current divergences and coastal region of the West Africa. Chlorophyll "a" concentration throughout the euphotic zone varied from 6 to 36 mg/m**3 and in the surface layer from 0.05 to 0.60 mg/m**3. Uneven distribution of primary production is due to physiological condition of phytoplankton.

(Table 2) Integrated concentration, production and dissolution of silica in the water column of the southern Pacific

An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.

Palynomorph concentrations in ODP Hole 105-645B samples (Table 1)

Significant changes in terrestrial and marine environments of Baffin Bay occurred throughout the late Pliocene to Holocene. Upper Pliocene and lowermost Pleistocene sediments contain abundant pollen and spores, which indicates the existence of open, coniferous, boreal forest to forest tundra in areas surrounding Baffin Bay. The late Pliocene-earliest Pleistocene also is characterized by relatively rich, dinoflagellate cyst and acritarch assemblages of boreal character, in which the dominance of Cymatiosphaera and Peridiniaceae may indicate neritic influx of sediments. In contrast, the late-early Pleistocene to Holocene interval is marked by a sparse terrestrial and marine palynoflora, with rare productive intervals. The general paucity of the Pleistocene palynoflora suggests low primary productivity, both on land and offshore, probably caused by cold, dry, high arctic conditions.