Stable isotopes, PCBs and pesticide concentrations in zooplankton, seawater and POM from Kongsfjorden and Liefdefjorden, Svalbard

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

San Francisco Coastal System grain size and geochemical data for sand provenance study

Over 150 million cubic meter of sand-sized sediment has disappeared from the central region of the San Francisco Bay Coastal System during the last half century. This enormous loss may reflect numerous anthropogenic influences, such as watershed damming, bay-fill development, aggregate mining, and dredging. The reduction in Bay sediment also appears to be linked to a reduction in sediment supply and recent widespread erosion of adjacent beaches, wetlands, and submarine environments. A unique, multi-faceted provenance study was performed to definitively establish the primary sources, sinks, and transport pathways of beach sized-sand in the region, thereby identifying the activities and processes that directly limit supply to the outer coast. This integrative program is based on comprehensive surficial sediment sampling of the San Francisco Bay Coastal System, including the seabed, Bay floor, area beaches, adjacent rock units, and major drainages. Analyses of sample morphometrics and biological composition (e.g., Foraminifera) were then integrated with a suite of tracers including 87Sr/86Sr and 143Nd/144Nd isotopes, rare earth elements, semi-quantitative X-ray diffraction mineralogy, and heavy minerals, and with process-based numerical modeling, in situ current measurements, and bedform asymmetry to robustly determine the provenance of beach-sized sand in the region.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

Body measurements and blood plasma lipid, PCB and OH-PCB content of polar bear (U. maritimus) mothers and cubs, Svalbard

The aim of this study was to examine the plasma concentrations and prevalence of polychlorinated biphenyls (PCBs) and hydroxylated PCB-metabolites (OH-PCBs) in polar bear (Ursus maritimus) mothers (n = 26) and their 4 months old cubs-of-the-year (n = 38) from Svalbard to gain insight into the mother-cub transfer, biotransformation and to evaluate the health risk associated with the exposure to these contaminants. As samplings were performed in 1997/1998 and 2008, we further investigated the differences in levels and pattern of PCBs between the two sampling years. The plasma concentrations of Sum(21)PCBs (1997/1998: 5710 ± 3090 ng/g lipid weight [lw], 2008: 2560±1500 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 228 ± 60 ng/g wet weight [ww], 2008: 80 ± 38 ng/g ww) in mothers were significantly lower in 2008 compared to in 1997/1998. In cubs, the plasma concentrations of Sum(21)PCBs (1997/1998: 14680 ± 5350 ng/g lw, 2008: 6070 ± 2590 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 98 ± 23 ng/g ww, 2008: 49 ± 21 ng/g ww) were also significantly lower in 2008 than in 1997/1998. Sum(21)PCBs in cubs was 2.7 ± 0.7 times higher than in their mothers. This is due to a significant maternal transfer of these contaminants. In contrast, Sum(6)OH-PCBs in cubs were approximately 0.53 ± 0.16 times the concentration in their mothers. This indicates a lower maternal transfer of OH-PCBs compared to PCBs. The majority of the metabolite/precursor-ratios were lower in cubs compared to mothers. This may indicate that cubs have a lower endogenous capacity to biotransform PCBs to OH-PCBs than polar bear mothers. Exposure to PCBs and OH-PCBs is a potential health risk for polar bears, and the levels of PCBs and OH-PCBs in cubs from 2008 were still above levels associated with health effects in humans and wildlife.

Geochemical analyses and Delta47 values in shallow water corals

Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Delta47) is a novel paleotemperature proxy based on the temperature dependent "clumping" of 13C-18O bonds. Similar ?47-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Delta47 vital effects. Here, we present the first systematic survey of Delta47 in shallow water corals. Sub-annual Red Sea Delta47 in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Delta47 values that consistently underestimate temperature by ~8 °C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Delta47 vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra- and inter-coral comparisons suggest that the deviation from expected Delta47 increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will complicate the interpretation of Delta47 as a paleothermometer in shallow water corals, it may still be a valuable paleoclimate proxy, particularly when applied as part of a multi-proxy approach.

Carbon, nitrogen and lipid content and egg and pellet production of female C. hyperboreus in situ and during incubation experiments

The effects of temperature and food availability on feeding and egg production of the Arctic copepod Calanus hyperboreus were investigated in Disko Bay, western Greenland, from winter to spring 2009. The abundance of females in the near bottom layer and the egg production of C. hyperboreus prior to the spring bloom document that reproduction relies on lipid stores. The maximum in situ egg production (± SE) of 54 ± 8 eggs female/d was recorded in mid-February at chlorophyll a concentrations below 0.1 µg/l, whereas no egg production was observed in mid-April when the spring bloom developed. After reproduction, the females migrated to the surface layer to exploit the bloom and refill their lipid stores. In 2 laboratory experiments, initiated before and during the spring bloom, mature females were kept with and without food at 5 different temperatures ranging from 0 to 10°C and the fecal pellet and egg production were monitored. Food had a clear effect on fecal pellet production but no effect on egg production, while temperature did not have an effect on egg or fecal pellet production in any of the experiments. Analyses of carbon and lipid content of the females before and after the experiments did not reflect any effect of food or temperature in the pre-bloom experiment, whereas in the bloom experiment a clear positive effect of food was detected in female biochemical profiles. The lack of a temperature response suggests a future warmer ocean could be unfavorable for C. hyperboreus compared to smaller Calanus spp. which are reported to exploit minor temperature elevations for increased egg production.

Age, body mass, mass change and dispersal distance of suckling and weaned grey seal (Halichoerus grypus) pups

Grey seal, Halichoerus grypus, pups in the breeding colony at Froan, Norway, have a bimodal pattern of early aquatic behaviour. About 40% of the pups spend their time ashore to save energy, which can be allocated to growth or deposition of energy-rich adipose tissue. The other 60% of the pups enter the sea during suckling and the early postweaning period, and disperse to other locations within the breeding colony. Pups may swim distances up to 12 km. Neonatal aquatic dispersal behaviour may lead to increased energy expenditure for thermoregulation and swimming, and thus lead to a low rate of body mass gain during suckling and a high rate of body mass loss after weaning. Thus, we examined relationships between natal aquatic dispersal behaviour and change in body mass (DeltaBM) in suckling and weaned pups. Suckling pups that had dispersed >2000 m had a significantly lower DBM than suckling pups that dispersed <2000 m or that did not disperse. In weaned pups, there were no effects of aquatic dispersal behaviour on DBM. We suggest that the bimodal natal aquatic dispersal behaviour in grey seals at the study site reflects two different strategies for postweaning survival: to stay ashore and get fat, or to take a swim and acquire diving and feeding skills.

Isotopic composition of diet and tissues, and isotope discrimination factors for pink-footed and barnacle geese, Svalbard

Breeding in the high Arctic is time constrained and animals should therefore start with their annual reproduction as early as possible. To allow for such early reproduction in migratory birds, females arrive at the breeding grounds either with body stores or they try to rapidly develop their eggs after arrival using local resources. Svalbard breeding barnacle geese Branta leucopsis have to fly non-stop for about 1100 km from their last continental staging site to the archipelago making the transport of body stores costly. However, environmental conditions at the breeding grounds are highly unpredictable favouring residual body stores allowing for egg production after arrival on the breeding grounds. We estimated the reliance on southern continental resources, i.e. body stores for egg formation, in barnacle geese using stable isotope ratios in the geese's forage along the flyway and in their eggs. Females adopted mixed breeding strategies by using southern resources as well as local resources to varying extents for egg formation. Southern capital in lipid-free yolk averaged 41% (range: 23-65%), early laid eggs containing more southern capital than eggs laid late in the season. Yolk lipids and albumen did not vary over time and averaged a southern capital proportion of 54% (range: 32-73%) and 47% (range: 25-88%), respectively. Our findings indicate that female geese vary the use of southern resources when synthesizing their eggs and this allocation also varies among egg tissues. Their mixed and flexible use of distant and local resources potentially allows for adaptive adjustments to environmental conditions encountered at the archipelago just before breeding.

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.

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.

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.

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.

Geochemistry of the water column of southern lake Baikal during 1967-2005

At present, when the influence of human economic activity is progressively increasing, significant attention is devoted to the state of water ecosystems. All researchers engaged in these problems agree that the state of the water system (pollution and eutrophication) can only be estimated on the basis of long-term researches. Systemic monitoring (at least once per month) of ionic components (Ca2+, Mg2+, Na+, K+, bicarbonates, sulfates, and chlorides) in unfiltered water of Lake Baikal and its tributaries had been carried out under the supervision of Votintsev since 1947. Based on the analysis of systematic data on trophic components obtained during 1965-2005, we tried to estimate the present-day trophic status of the pelagic zone in the lake, define the trend of long-term changes of trophic components and understand the reasons of the distortion of cyclicity in the development of spring diatom algae, which create a favorable environment in any water basin. It should be noted that the station near Cape Polovinnyi is located 20 km away from the town of Baikal'sk. Wastewaters of the Baikal'sk pulp and paper mill is the main source of dioxins and furans in Baikal. Based on the significant difference between sulfate contents in wastewaters of the plant (>300 mg/l), tributaries of Baikal (7.5 mg/l), and waters in the southern part of the lake (3.9 mg/l), we defined the following periods: (i) period of natural seasonal patterns until 1967-1968 (prior to putting the Baikal'sk Mill into operation; (ii) period of weak anthropogenic pollution (1969-1985); and (iii) period of strong anthropogenic pollution since 1986.

Geochemistry of tephra from Lake Ohrid

Here we present a tephrostratigraphic record (core Co1202) recovered from the northeastern part of Lake Ohrid (Republics of Macedonia and Albania) reaching back to Marine Isotope Stage (MIS) 6. Overall ten horizons (OT0702-1 to OT0702-10) containing volcanic tephra have been recognised throughout the 14.94 m long sediment succession. Four tephra layers were visible at macroscopic inspection (OT0702-4, OT0702-6, OT0702-8 and OT0702-9), while the remaining six are cryptotephras (OT0702-1, OT0702-2, OT0702-3, OT0702-5, OT0702-7 and OT0702-10) identified from peaks in K, Zr and Sr intensities, magnetic susceptibility measurements, and washing and sieving of the sediments. Glass shards of tephra layers and cryptotephras were analysed with respect to their major element composition, and correlated to explosive eruptions of Italian volcanoes. The stratigraphy and the major element composition of tephra layers and cryptotephras allowed the correlation of OT0702-1 to AD 472 or AD 512 eruptions of Somma-Vesuvius, OT0702-2 to the FL eruption of Mount Etna, OT0702-3 to the Mercato from Somma-Vesuvius, OT0702-4 to SMP1-e/Y-3 eruption from the Campi Flegrei caldera, OT0702-5 to the Codola eruption (Somma-Vesuvius or Campi Flegrei), OT0702-6 to the Campanian Ignimbrite/Y-5 from the Campi Flegrei caldera, OT0702-7 to the Green Tuff/Y-6 eruption from Pantelleria Island, OT0702-8 to the X-5 eruption probably originating from the Campi Flegrei caldera, OT0702-9 to the X-6 eruption of generic Campanian origin, and OT0702-10 to the P-11 eruption from Pantelleria Island. The fairly well-known ages of these tephra layers and parent eruptions provide new data on the dispersal and deposition of these tephras and, furthermore, allow the establishment of a chronological framework for core Co1202 for a first interpretation of major sedimentological changes.

Hydrogen isotope compositions of terrestrial plant-wax n-alkanes analysed on a transect of marine surface sediment samples from 1°N to 28°S off southwest Africa

A transect of marine surface sediment samples from 1° N to 28° S off southwest Africa was analysed to verify the application of hydrogen isotope compositions of terrestrial plant-wax n-alkanes preserved in ocean sediments as a proxy for continental hydrological conditions. Conditions on the adjacent continent range from humid evergreen forests to deciduous forests, wood- and shrub land and further to arid grasslands and deserts. The hydrogen isotope values for the dominant n-alkane homologues (C29, C31 and C33) vary from -123 per mil to -141 per mil VSMOW and correlate with the modelled hydrogen isotope composition of mean annual and growing season precipitation of postulated continental source areas (r up to 0.8, p < 0.01). The apparent hydrogen isotope fractionation between alkanes and mean annual precipitation is remarkably uniform (-109 per mil on average, Sigma <= 5 per mil, n = 27). Potentially, effects of aridity on the apparent hydrogen isotope fractionation are concealed by the contribution of different plants (C3 dicotyledons vs C4 grasses). Thus, isotope ratios of leaf wax n-alkanes preserved in ocean margin sediments in these and similar tropical regions may be directly converted to dD ratios of ancient precipitation by employing a constant hydrogen isotope fractionation.