Mercury content and isotopic composition of frost flower, surface snow and brine samples near Barrow, Alaska

Frost flowers are ice crystals that grow on refreezing sea ice leads in Polar Regions by wicking brine from the sea ice surface and accumulating vapor phase condensate. These crystals contain high concentrations of mercury (Hg) and are believed to be a source of reactive halogens, but their role in Hg cycling and impact on the fate of Hg deposited during atmospheric mercury depletion events (AMDEs) are not well understood. We collected frost flowers growing on refreezing sea ice near Barrow, Alaska (U.S.A.) during an AMDE in March 2009 and measured Hg concentrations and Hg stable isotope ratios in these samples to determine the origin of Hg associated with the crystals. We observed decreasing Delta199Hg values in the crystals as they grew from new wet frost flowers (mean Delta199Hg = 0.77 ± 0.13 per mil, 1 s.d.) to older dry frost flowers (mean Delta199Hg = 0.10 ± 0.05 per mil, 1 s.d.). Over the same time period, mean Hg concentrations in these samples increased from 131 ± 6 ng/L (1 s.d.) to 180 ± 28 ng/L (1 s.d.). Coupled with a previous study of Hg isotopic fractionation during AMDEs, these results suggest that Hg initially deposited to the local snowpack was subsequently reemitted during photochemical reduction reactions and ultimately accumulated on the frost flowers. As a result of this process, frost flowers may lead to enhanced local retention of Hg deposited during AMDEs and may increase Hg loading to the Arctic Ocean.

Granulometry, geochemistry, amino acids, radiocarbon ages and paleomagnetics of samples from Heidemann Valley

A Pliocene (2.6-3.5 Ma) age is determined from glacial sediments studied in a 20m long, 4 m deep trench excavated in Heidemann Valley, Vestfold Hills, East Antarctica. The age determination is based on a combined study of amino acid racemization, diatoms, foraminifera, and magnetic polarity, and supports earlier estimates of the age of the sedimentary section; all are beyond 14C range. Four till units are recognized and documented, and 16 subunits are identified. All are ascribed to deposition during a Late Pliocene glaciation that was probably the last time the entire Vestfold Hills was covered by an enlarged East Antarctic Ice Sheet (EAIS). Evidence for other more recent glacial events of the 'Vestfold Glaciation' may have been due to lateral expansion of the Sorsdal Glacier and limited expansion of the icesheet margin during the Last Glacial Maximum rather than a major expansion of the EAIS. The deposit appears to correlate with a marine deposition event recorded in Ocean Drilling Program Site 1166 in Prydz Bay, possibly with the Bardin Bluffs Formation of the Prince Charles Mountains and with part of the time represented in the ANDRILL AND-1B core in the Ross Sea.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Concentrations of brominated and chlorinated contaminants in adipose tissue of polar bears (Ursus maritimus) between 1991-2007

Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, sum DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); alpha-hexachlorocyclohexane (alpha-HCH) decreased (-11%/year); beta-HCH increased ( + 8.3%/year); and sum PCB and sum chlordane (CHL), both contaminants at highest concentrations in all years (>1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (-1.6%/year to -6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). sum chlorobenzene, octachlorostyrene, sum mirex, sum MeSO2-PCB and dieldrin did not significantly change. Increasing sum PBDE levels (+13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(alpha)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or "weathering" of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year. DDT patterns were not associated with any explanatory variables, possibly related to local DDT sources. Contaminant pattern trends may be useful in distinguishing the possible role of ecological/diet changes on contaminant burdens from expected dynamics due to atmospheric sources and weathering.

Meiofauna of surface sediments in the Cretan Sea

Quantitative information on metazoan meiofaunal abundance and biomass was obtained from three continental shelf (at 40, 100 and 200 m depth) and four deep-sea stations (at 540, 700, 940 and 1540 m depth) in the Cretan Sea (South Aegean Sea, NE Mediterranean). Samples were collected on a seasonal basis (from August 1994 to September 1995) with the use of a multiple corer. Meiofaunal abundance and biomass on the continental shelf of the Cretan Sea were high, in contrast to the extremely low values reported for the bathyal sediments that showed values comparable to those reported for abyssal and hadal environments. In order to explain the spatial and seasonal changes in metazoan meiofauna these data were compared with: (1) the concentrations of 'food indicators' (such as proteins, lipids, soluble carbohydrates and CPE) (2) the bacterial biomass (3) the flux of labile organic compounds to the sea floor at a fixed station (D7, 1540 m depth). Highly significant relationships between meiofaunal parameters and CPE, protein and lipid concentrations and bacterial biomass were found. Most of the indicators of food quality and quantity (such as CPE, proteins and carbohydrates) showed a clear seasonality with highest values in February and lowest in September. Such changes were more evident on the continental shelf rather than at deeper depths. On the continental shelf, significant seasonal changes in meiofaunal density were related to changes in the input of labile organic carbon whereas meiofaunal assemblages on the deep-sea stations showed time-lagged changes in response to the food input recorded in February 95. At all deep-sea stations meiofaunal density increased with a time lag of 2 months. Indications for a time-lagged meiofaunal response to the food inputs were also provided by the increase in nauplii densities during May 95 and the increase in individual biomass of nematodes, copepods and polychaetes between February and May 1995. The lack of strong seasonal changes in deep sea meiofaunal density suggests that the supply of organic matter below 500 m is not strong enough to support a significant meiofaunal development. Below 700 m depth >92% of the total biomass in the sediment was represented by bacteria. The ratio of bacterial to meiofaunal biomass increased with increasing water depth indicating that bacteria are probably more effective than meiofauna in exploiting refractory organic compounds. These data lead us to hypothesise that the deep-sea sediments of the Cretan Sea are largely dependent upon a benthic microbial loop.

Mass balances of different sectors in Antarctica in 1996, 2000 and 2006

Large uncertainties remain in the current and future contribution to sea level rise from Antarctica. Climate warming may increase snowfall in the continent's interior, but enhance glacier discharge at the coast where warmer air and ocean temperatures erode the buttressing ice shelves. Here, we use satellite interferometric synthetic-aperture radar observations from 1992 to 2006 covering 85% of Antarctica's coastline to estimate the total mass flux into the ocean. We compare the mass fluxes from large drainage basin units with interior snow accumulation calculated from a regional atmospheric climate model for 1980 to 2004. In East Antarctica, small glacier losses in Wilkes Land and glacier gains at the mouths of the Filchner and Ross ice shelves combine to a near-zero loss of 4 ± 61 Gt/yr. In West Antarctica, widespread losses along the Bellingshausen and Amundsen seas increased the ice sheet loss by 59% in 10 years to reach 132 ± 60 Gt/yr in 2006. In the Peninsula, losses increased by 140% to reach 60 ± 46 Gt/yr in 2006. Losses are concentrated along narrow channels occupied by outlet glaciers and are caused by ongoing and past glacier acceleration. Changes in glacier flow therefore have a significant, if not dominant impact on ice sheet mass balance.

Fatty acid composition of tissue samples from Arctic walruses (Odobenus rosmarus rosmarus) and their prey

Blubber biopsies were collected from 18 adult male walruses from Svalbard, Norway. The biopsies were taken vertically through the skin and the entire blubber layer down to, but not including, the muscle layer. Fatty acid (FA) compositions of inner blubber, outer blubber and dermis of the walruses and of potential prey organisms were determined. The three layers differed significantly from one another in FA composition. Generally, the inner blubber contained more long-chained monounsaturated, saturated and polyunsaturated FAs, while the outer blubber and dermis contained more short-chained monounsaturated FAs. This stratification is similar to what has been observed in other marine mammal species. However, differences between layers were less pronounced than in most other species, possibly because the extremely thick overlying dermis of walruses provides an insulating shield, which affects the FA composition of the outer blubber. The FA composition of the potential prey organisms was different from that of the blubber of the walruses, although more similar to the inner blubber than to the outer blubber or dermis. FA composition in the inner blubber was not significantly correlated with age (assessed by tusk volume), while the FA composition of the outer blubber and dermis were significantly correlated with age.

Brominated flame retardants and biomagnification factors in marine species in the North-East Atlantic

BACKGROUND: Concentrations of brominated flame retardants (BFRs) are reported to increase in marine ecosystems. OBJECTIVES: Characterize exposure to BFRs in animals from different trophic levels in North-East Atlantic coastal marine ecosystems along a latitudinal gradient from southern Norway to Spitsbergen, Svalbard, in the Arctic. Calanoid species were collected from the Oslofjord (59°N), Froan (64°N), and Spitsbergen (> 78°N); Atlantic cod (Gadus morhua) from the Oslofjord and Froan; polar cod (Boreogadus saida) from Bear Island (74°N) and Spitsbergen; harbor seal (Phoca vitulina) from the Oslofjord, Froan, and Spitsbergen; and ringed seal (Phoca vitulina) from Spitsbergen. Eggs of common tern (Sterna hirundo) were collected from the Oslofjord, and eggs of arctic terns (Sterna paradisaea) from Froan and Spitsbergen. RESULTS: Levels of polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD) generally decreased as a function of increasing latitude, reflecting distance from release sources. The clear latitudinal decrease in levels of BFRs was not pronounced in the two tern species, most likely because they are exposed during migration. The decabrominated compound BDE-209 was detected in animals from all three ecosystems, and the highest levels were found in arctic tern eggs from Spitsbergen. HBCD was found in animals from all trophic levels, except for in calanoids at Froan and Spitsbergen. CONCLUSIONS: Even though the levels of PBDEs and HBCD are generally low in North-East Atlantic coastal marine ecosystems, there are concerns about the relatively high presence of BDE-209 and HBCD.

Sea surface temperature reconstruction for sediment core M35003-4 in the western tropical North Atlantic

Planktonic foraminiferal census counts are used to construct high-resolution sea surface temperature (SST) and subsurface (thermocline) temperature records at a core site in the Tobago Basin, Lesser Antilles. The record is used to document climatic variability at this tropical site in comparison to middle- and high-latitude sites and to test current concepts of cross-equatorial heat transports as a major player in interhemispheric climate variability. Temperatures are estimated using transfer function and modern analog techniques. Glacial - maximum cooling of 2.5°-3°C is indicated; maximum cooling by 4°C is inferred for isotope stage 3. The SST record displays millennial-scale variability with temperature jumps of up to 3°C and closely tracks the structure of ice-core Dansgaard/Oeschger cycles. SST variations in part of the record run opposite to the SST evolution at high northern latitude sites, pointing to thermohaline circulation and marine heat transport as an important factor driving SST in the tropical and high-latitude Atlantic, both on orbital and suborbital timescales.

Radiocarbon dating, carbon storage and soil properties of samples from Tulemalu Lake, central Canadian Arctic

We investigated total storage and landscape partitioning of soil organic carbon (SOC) in continuous permafrost terrain, central Canadian Arctic. The study is based on soil chemical analyses of pedons sampled to 1 m depth at 35 individual sites along three transects. Radiocarbon dating of cryoturbated soil pockets, basal peat and fossil wood shows that cryoturbation processes have been occurring since the Middle Holocene and that peat deposits started to accumulate in a forest-tundra environment where spruce was present (~6000 cal yrs BP). Detailed partitioning of SOC into surface organic horizons, cryoturbated soil pockets and non-cryoturbated mineral soil horizons is calculated (with storage in active layer and permafrost calculated separately) and explored using principal component analysis. The detailed partitioning and mean storage of SOC in the landscape are estimated from transect vegetation inventories and a land cover classification based on a Landsat satellite image. Mean SOC storage in the 0-100 cm depth interval is 33.8 kg C/m**2, of which 11.8 kg C/m**2 is in permafrost. Fifty-six per cent of the total SOC mass is stored in peatlands (mainly bogs), but cryoturbated soil pockets in Turbic Cryosols also contribute significantly (17%). Elemental C/N ratios indicate that this cryoturbated soil organic matter (SOM) decomposes more slowly than SOM in surface O-horizons.

Stable oxygen and carbon isotopes ratios of sediment core GeoB9528-3

The carbon isotopic composition of individual plant leaf waxes (a proxy for C3 vs. C4 vegetation) in a marine sediment core collected from beneath the plume of Sahara-derived dust in northwest Africa reveals three periods during the past 192,000 years when the central Sahara/Sahel contained C3 plants (likely trees), indicating substantially wetter conditions than at present. Our data suggest that variability in the strength of Atlantic meridional overturning circulation (AMOC) is a main control on vegetation distribution in central North Africa, and we note expansions of C3 vegetation during the African Humid Period (early Holocene) and within Marine Isotope Stage (MIS) 3 (approx. 50-45 ka) and MIS 5 (approx. 120-110 ka). The wet periods within MIS 3 and 5 coincide with major human migration events out of sub-Saharan Africa. Our results thus suggest that changes in AMOC influenced North African climate and, at times, contributed to amenable conditions in the central Sahara/Sahel, allowing humans to cross this otherwise inhospitable region.

Paleoclimate records from maar Monticchio

Oxygen-isotope records from Greenland ice cores indicate numerous rapid climate fluctuations during the last glacial period. North Atlantic marine sediment cores show comparable variability in sea surface temperature and the deposition of icerafted debris. In contrast, very few continental records of this time period provide the temporal resolution and environmental sensitivity necessary to reveal the extent and effects of these environmental fluctuations on the continents. Here we present high-resolution geochemical, physical and pollen data from lake sediments in Italy and from a Mediterranean sediment core, linked by a common tephrochronology. Our lacustrine sequence extends to the past 102,000 years. Many of its features correlate well with the Greenland ice-core records, demonstrating that the closely coupled ocean-atmosphere system of the Northern Hemisphere during the last glacial extended its influence at least as far as the central Mediterranean region. Numerous vegetation changes were rapid, frequently occurring in less than 200 years, showing that the terrestrial biosphere participated fully in lastglacial climate variability. Earlier than 65,000 years ago, our record shows more climate fluctuations than are apparent in the Greenland ice cores. Together, the multi-proxy data from the continental and marine records reveal differences in the seasonal character of climate during successive interstadials, and provide a step towards determining the underlying mechanisms of the centennial-millennial-scale variability.

Lead/Calcium profiles in the common time window 1770-2010 of the three Arctica islandica shells

In the study, we establish centennial records of anthropogenic lead pollution at different locations in the North Atlantic (Iceland, USA, and Europe) by means of lead deposited in shells of the long-lived bivalve Arctica islandica. Due to local oceanographic and geological conditions we conclude that the lead concentrations in the Icelandic shell reflect natural influxes of lead into Icelandic waters. In comparison, the lead profile of the US shell is clearly driven by anthropogenic lead emissions transported from the continent to the ocean by westerly surface winds. Lead concentrations in the European North Sea shell, in contrast, are dominantly driven by local lead sources resulting in a much less conspicuous 1970s gasoline lead peak. In conclusion, the lead profiles of the three shells are driven by different influxes of lead, and yet, all support the applicability of Pb/Ca analyses of A. islandica shells to reconstruct location specific anthropogenic lead pollution.

Geochemistry of Chixulub ejecta in ODP Leg 207 holes

An up to 2-cm thick Chicxulub ejecta deposit marking the Cretaceous-Paleogene (K-Pg) boundary (the "K-T" boundary) was recovered in six holes drilled during ODP Leg 207 (Demerara Rise, tropical western Atlantic). Stunning features of this deposit are its uniformity over an area of 30 km2 and the total absence of bioturbation, allowing documentation of the original sedimentary sequence. High-resolution mineralogical, petrological, elemental, isotopic (Sr-Nd), and rock magnetic data reveal a distinct microstratigraphy and a range of ejecta components. The deposit is normally graded and composed predominantly of rounded, 0.1- to max. 1-mm sized spherules. Spherules are altered to dioctahedral aluminous smectite, though occasionally relict Si-Al-rich hydrated glass is also present, suggesting acidic precursor lithologies. Spherule textures vary from hollow to vesicle-rich to massive; some show in situ collapse, others include distinct Fe-Mg-Ca-Ti-rich melt globules and lath-shaped Al-rich quench crystals. Both altered glass spherules and the clay matrix (Site 1259B) display strongly negative epsilon-Nd (T=65Ma) values (-17) indicating uptake of Nd from contemporaneous ocean water during alteration. Finally, Fe-Mg-rich spherules, shocked quartz and feldspar grains, few lithic clasts, as well as abundant accretionary and porous carbonate clasts are concentrated in the uppermost 0.5-0.7 mm of the deposit. The carbonate clasts display in part very unusual textures, which are interpreted to be of shock-metamorphic origin. The preservation of delicate spherule textures, normal grading with lack of evidence for traction transport, and sub-millimeter scale compositional trends provide evidence for this spherule deposit representing a primary air-fall deposit not affected by significant reworking. The ODP Leg 207 spherule deposit is the first known dual-layer K-Pg boundary in marine settings; it incorporates compositional and stratigraphic aspects of both proximal and distal marine sites. Its stratigraphy strongly resembles the dual-layer K-Pg boundary deposits in the terrestrial Western Interior of North America (although there carbonate phases are not preserved). The occurrence of a dual ejecta layer in these quite different sedimentary environments - separated by several thousands of kilometers - provides additional evidence for an original sedimentary sequence. Therefore, the layered nature of the deposit may document compositional differences between ballistic Chicxulub ejecta forming the majority of the spherule deposit, and material falling out from the vapor (ejecta) plume, which is concentrated in the uppermost part.

Water chemistry, carbonate system parameters, and macro-organism biomass of vent and off-vent sites in the Columbretes Islands Marine Reserve

Ocean acidification is receiving increasing attention because of its potential to affect marine ecosystems. Rare CO2 vents offer a unique opportunity to investigate the response of benthic ecosystems to acidification. However, the benthic habitats investigated so far are mainly found at very shallow water (less than or equal to 5 m depth) and therefore are not representative of the broad range of continental shelf habitats. Here, we show that a decrease from pH 8.1 to 7.9 observed in a CO2 vent system at 40 m depth leads to a dramatic shift in highly diverse and structurally complex habitats. Forests of the kelp Laminaria rodriguezii usually found at larger depths (greater than 65 m) replace the otherwise dominant habitats (i.e. coralligenous outcrops and rhodolith beds), which are mainly characterized by calcifying organisms. Only the aragonite-calcifying algae are able to survive in acidified waters, while high-magnesium-calcite organisms are almost completely absent. Although a long-term survey of the venting area would be necessary to fully understand the effects of the variability of pH and other carbonate parameters over the structure and functioning of the investigated mesophotic habitats, our results suggest that in addition of significant changes at species level, moderate ocean acidification may entail major shifts in the distribution and dominance of key benthic ecosystems at regional scale, which could have broad ecological and socio-economic implications.