(Supplement) Concentration in palynomorphs per gram of dry sediment in ANDRILL core AND-2A

An exceptional triple palynological signal (unusually high abundance of marine, freshwater, and terrestrial palynomorphs) recovered from a core collected during the 2007 ANDRILL (Antarctic geologic drilling program) campaign in the Ross Sea, Antarctica, provides constraints for the Middle Miocene Climatic Optimum. Compared to elsewhere in the core, this signal comprises a 2000-fold increase in two species of dinoflagellate cysts, a synchronous five-fold increase in freshwater algae, and up to an 80-fold increase in terrestrial pollen, including a proliferation of woody plants. Together, these shifts in the palynological assemblages ca. 15.7 Ma ago represent a relatively short period of time during which Antarctica became abruptly much warmer. Land temperatures reached 10 °C (January mean), estimated annual sea-surface temperatures ranged from 0 to 11.5 °C, and increased freshwater input lowered the salinity during a short period of sea-ice reduction.

Water temperature, salinity, DOC content and THNS concentration in samples taken during POLARSTERN cruise to the Fram Strait and Greenland Sea

Dissolved organic matter (DOM) was isolated with XAD-2 and 4 resins from different water masses of the Greenland Sea and Fram Strait. The contribution of XAD-extractable dissolved organic carbon (DOC), operationally defined as 'recalcitrant' or humic substances, to total DOC was in the range of 45 ± 9% in surface waters and 60 ± 6% in deep waters. The carbohydrate concentration and composition were determined using the l-tryptophan/sulfuric acid method (for the bulk carbohydrate concentration, TCHO) and high performance anion-exchange chromatography after sulfuric acid hydrolysis (for the distribution of total hydrolysable neutral sugars, THNS). Carbohydrates contributed up to 6.8% to both total and recalcitrant DOC. TCHO contribution to total DOC decreased with depth from on average 4.1 ± 1.2% in surface waters to 2.2 ± 1.0% in deep waters, whereas the THNS contribution was similar in both layers, accounting for 2.5 ± 1.6% (surface) and 2.4 ± 0.2% (at depth). TCHO contribution to XAD-extractable DOC also decreased with depth from 4.5 ± 1.7% to 2.1 ± 1.0%, whereas THNS contribution was almost constant, with yields of 0.5 ± 0.3% for surface samples and 0.6 ± 0.1% at depth. The molecular size distribution of the recalcitrant DOM showed for all fractions a clear trend towards small molecules in the deep sea. More than half of the XAD-extractable carbohydrates of surface samples and more than 70% of deep sea samples were found in the nonpolar fraction from XAD, which was eluted with methanol. Glucose was the dominant carbohydrate in the surface water samples, whereas in the deep sea the composition was more uniform. In the XAD extracts, the compositions were less variable than in the original samples. The neutral sugar composition, in particular glucose and the deoxysugars, is indicative of the diagenetic state of the extracted DOM. The molar ratio (fucose + rhamnose)/(arabinose + xylose) was lowest for deep sea extractable DOM, indicating a high contribution of material modified by microorganisms. The THNS composition and distribution reveal that "recalcitrant" carbohydrates are heteropolysaccharides, carbohydrate units incorporated into a framework of a highly nonpolar structure with a lack of functional groups.

Lithium concentration in manganese nodules of the Pacific Ocean (Hakurei Maru Cruise GH77-1, January-March, 1977)

Various manganese nodules donated to the Scripps Institution of Oceanography from the Hakurei Maru Cruise GH77-1, January-March, 1977, in the Central Pacific Basin have been analysed for their lithium content by J. Korkish from the Institute of Analytical Chemistry, Analysis of Nuclear Raw Materials Division, University of Vienna, Austria. The author has used a Perkin-Elmer atomic-absorption spectrometer 303 after speration by dissolution in hydrochloric acid.

(Table 2) Mercury concentration in hair of Northwest Greenland polar bears (Ursus maritimus)

Hair samples from 117 Northwest Greenland polar bears (Ursus maritimus) were taken during 1892-2008 and analyzed for total mercury (hereafter Hg). The sample represented 28 independent years and the aim of the study was to analyze for temporal Hg trends. Mercury concentrations showed yearly significant increases of 1.6-1.7% (p < 0.0001) from 1892 to 2008 and the two most recent median concentrations from 2006 and 2008 were 23- to 27-fold higher respectively than baseline level from 1300 A.D. in the same region (Nuullit). This indicates that the present (2006-2008) Northwest Greenland polar bear Hg exposure is 95.6-96.2% anthropogenic in its origin. Assuming a continued anthropogenic increase, this model estimated concentrations in 2050 and 2100 will be 40- and 92-fold the baseline concentration, respectively, which is equivalent to a 97.5 and 98.9% man-made contribution. None of the 2001-2008 concentrations of Hg in Northwest Greenland polar bear hair exceeded the general guideline values of 20-30 µg/g dry weight for terrestrial wildlife, whereas the neurochemical effect level of 5.4 µg Hg/g dry weight proposed for East Greenland polar bears was exceeded in 93.5% of the cases. These results call for detailed effect studies in main target organs such as brain, liver, kidney, and sexual organs in the Northwest Greenland polar bears.

(Table T1) Iridium concentration in ODP Site 177-1090 sediments

Anomalous concentrations of Ir have been found in upper Eocene sediments from Ocean Drilling Program (ODP) Hole 1090B. Clear and dark-colored spherules that are believed to be microtektites and clinopyroxene-bearing microkrystites, respectively, were found in the samples with highest Ir. The peak Ir concentration in Sample 177-1090B-30X-5,105-106 (954 pg/g) and the net Ir fluence (14 ng/cm**2) at this site are higher than at most other localities except for Caribbean site RC9-58. The Ir anomaly and impact debris are probably correlative with similar deposits found at ODP Site 689 on the Maude Rise and at other localities around the world.

(Table 1) Li, B and Sr isotopic composition and concentration in ODP Leg 209 samples

Spinel harzburgites from ODP Leg 209 (Sites 1272A, 1274A) drilled at the Mid-Atlantic ridge between 14°N and 16°N are highly serpentinized (50-100%), but still preserve relics of primary phases (olivine >= orthopyroxene >> clinopyroxene). We determined whole-rock B and Li isotope compositions in order to constrain the effect of serpentinization on d11B and d7Li. Our data indicate that during serpentinization Li is leached from the rock, while B is added. The samples from ODP Leg 209 show the heaviest d11B (+29.6 to +40.52 per mil) and lightest d7Li (-28.46 to +7.17 per mil) found so far in oceanic mantle. High 87Sr/86Sr ratios (0.708536 to 0.709130) indicate moderate water/rock ratios (3 to 273, on the average 39), in line with the high degree of serpentinization observed. Applying the known fractionation factors for 11B/10B and 7Li/6Li between seawater and silicates, serpentinized peridotite in equilibrium with seawater at conditions corresponding to those of the studied drill holes (pH: 8.2; temperature: 200 °C) should have d11B of +21.52 per mil and d7Li of +9.7 per mil. As the data from ODP Leg 209 are clearly not in line with this, we modelled a process of seawater-rock interaction where d11B and d7Li of seawater evolve during penetration into the oceanic plate. Assuming chemical equilibrium between fluid and a rock with d11B and d7Li of ODP Leg 209 samples, we obtain d11B and d7Li values of +50 to +60 per mil, -2 to +12 per mil, respectively, for the coexisting fluid. In the oceanic domain, no hydrothermal fluids with such high d11B have yet been found, but are predicted by theoretical calculations. Combining the calculated water/rock ratios with the d7Li and d11B evolution in the fluid, shows that modification of d7Li during serpentinization requires higher water/rock ratios than modification of d11B. Extremely heavy d11B in serpentinized oceanic mantle can potentially be transported into subduction zones, as the B budget of the oceanic plate is dominated by serpentinites. Extremely light d7Li is unlikely to survive as the Li budget is dominated by the oceanic crust, even at small fractions.

Concentrations of natural and anthropogenic organohalogens in water and air samples in the Canadian Arctic during IPY (2007-2008)

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg/L) were as follows: alpha-hexachlorocyclohexane (alpha-HCH) 465-1013, gamma-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg/m**3) were as follows: alpha-HCH 7.5-48, gamma-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4-39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of alpha-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The alpha-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic alpha-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng/m**2/d) were as follows: alpha-HCH 6.8 ± 3.2 (2.7-13), gamma-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng/m**2/d (-1.6 to 2.0).

(Table 2) Concentration of phytoplankton pigments in Adventfjorden in spring and summer of 1997

The study was carried out from April 30 until July 13 of 1997 in Adventfjorden (Spitsbergen). Formation of a less saline and warmer surface water (~1 m thick) caused by melting of the ice was observed in the fjord during the first days of May. In summer the less saline surface layer was about 3 m thick. Euphotic depth measured under the ice sheet reached 12 m, whereas load of mineral matter brought with riverine discharge in summer (content of total particulate matter in the fjord reached 1.66 kg/m**2) dramatically reduced euphotic zone depth to 0.35 m. By pigment measurement three phases of phytoplankton development in Adventfjorden were distinguished: (1) spring bloom that has started under fast ice and reached maximum in the mid of May, (2) stagnation period in June, (3) increase of pigment concentration in July, what could indicate start of the next algae bloom. Analyses of chlorophylls and carotenoids revealed that diatoms (chl c, fucoxanthin), and green algae (chl b, lutein) dominated phytoplankton community in the fjord. Moreover, presence of peridinin indicates presence of Dinophyta and alloxanthin - occurence of Cryptophyta. In May and June 1997 phytoplankton appeared mainly in the surface of water, while in July, as a result of inflow of turbulent riverine waters into Adventfjorden, algae cells were pushed down and the highest numbers were observed at depth ~20 m. Great phaeopigments to chl a ratio (= 0.54) found in fjord seston in June and July probably shows strong impact of zooplankton grazing on phytoplankton development. High contribution of chlorophyllide a in porphyrin a poll in samples collected under fast ice (chlorophyllide a / chl a ratio = 0.18) reflects the final stage of algal communitie succession in ice, just before spring ice melt and release of biota to oceanic water. Chlorophyllide a content during summer was minor or not detectable, demonstrating that diatom cells were in good physiological condition. High chl a allomer / chl a ratio (average = 0.11 for the period investigated) confirms high oxygen concentration in environment of Adventfjorden.

Composition of aerosols collected in the Western Russian Arctic in August-September 1991

In August-September 1991 during the SPASIBA expedition (Scientific Program on the Arctic and Siberian Aquatorium) aboard R/V Yakov Smirnitzky in the Laptev Sea ten samples of aerosols were collected by nylon nets. A combined approach including various analytical techniques, such as single-particle analysis, instrumental neutron activation analysis, and atomic absorption spectrophotometry, was used to study composition of the samples. Mass concentration of coarse-grained (>0.001 mm) insoluble fraction of aerosols ranged from 80 to 460 ng/m**3. In all the samples remains of land vegetation were found to be the dominant component. Organic carbon content of the aerosols ranged from 23 to 49%. Inorganic part of the samples was represented mainly by alumosilicates and quartz. Anthropogenic ''fly ash'' particles were observed in all the samples. Temporal variations of element concentrations resulted from differences in air masses entering the studied area.

The distribution of zinc, cadmium, copper and iron in seawater of the Iceland-Faroe Ridge area

During the International ICES Expedition "Overflow '73" a total of 174 samples from 18 stations were collected by R. V. "Meteor" in the waters of the Iceland-Faroe Ridge area. They were filtered on board ship (through 0.4 mym "Nuclepore" filters), then stored in 500 cm**3 quartz bottles (at -20 °C) and analyzed in air-filtered laboratories on land for zinc and cadmium by means of the differential pulse anodic stripping voltammetry technique and copper and iron by flameless atomic absorption spectrometry. The overall averages of 1.9 myg Zn l**-1, 0.07 myg Cd l**-1, 0.5 myg Cu l**-1 and 0.9 myg Fe l**-1 are in good agreement with recent "baseline" studies of open-ocean waters. The mixture of low salinity water masses from the North Iceland Shelf/Arctic Intermediate Waters seem to maintain distinctly lower concentration of Cd, Cu and Fe than the waters from the North Atlantic and the Norwegian Sea where quite similar mean values are found. There is only little evidence for the assumption that overflow events on the ridge are influencing the concentrations of dissolved metals in the near-bottom layers.

Concentration of organic compounds in slush, under-ice water, and the snow-ice fast-ice cover of the southeast sector of the Antarctic in April 2008

Data are presented on concentration of hydrocarbons (HC) relative to concentrations of suspended matter, lipids, organic carbon, and chlorophyll a in surface waters and snow-ice cover of the East Antarctic coastal areas. It was shown that growth of concentrations of aliphatic HC (AHC) to 30 µg/l in surface waters takes place in frontal zones and under young ice formation. AHC concentration in snow increases with growth of aerosol concentration in the atmosphere. In the lower part of ice, at the boundary with seawater, despite low temperatures, autochthonous processes may provide high AHC concentrations (up to 289 µg/l). Within the snow-ice cover on fast ice, concentration co-variations of all the compounds considered take place.