Isotopic signatures and mercury content of arctic char and their prey, and water chemistry of 18 arctic Canadian lakes

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to d13C and d15N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The d13C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 ± 1.1 to 64.3 ± 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.

Ages and isotopic signatures of peat cores from a boreal landscape, Interior Alaska

To determine the influence of fire and thermokarst in a boreal landscape, we investigated peat cores within and adjacent to a permafrost collapse feature on the Tanana River Floodplain of Interior Alaska. Radioisotope dating, diatom assemblages, plant macrofossils, charcoal fragments, and carbon and nitrogen content of the peat profile indicate ~600 years of vegetation succession with a transition from a terrestrial forest to a sedge-dominated wetland over 100 years ago, and to a Sphagnum-dominated peatland in approximately 1970. The shift from sedge to Sphagnum, and a decrease in the detrended tree-ring width index of black spruce trees adjacent to the collapse coincided with an increase in the growing season temperature record from Fairbanks. This concurrent wetland succession and reduced growth of black spruce trees indicates a step-wise ecosystem-level response to a change in regional climate. In 2001, fire was observed coincident with permafrost collapse and resulted in lateral expansion of the peatland. These observations and the peat profile suggest that future warming and/or increased fire disturbance could promote permafrost degradation, peatland expansion, and increase carbon storage across this landscape; however, the development of drought conditions could reduce the success of both black spruce and Sphagnum, and potentially decrease the long-term ecosystem carbon storage.

(Table 1) Stable carbon and nitrogen isotopic ratios of potential prey species of bearded seals (Erignathus barbatus), Svalbard

Changing patterns of sea-ice distribution and extent have measurable effects on polar marine systems. Beyond the obvious impacts of key-habitat loss, it is unclear how such changes will influence ice-associated marine mammals in part because of the logistical difficulties of studying foraging behaviour or other aspects of the ecology of large, mobile animals at sea during the polar winter. This study investigated the diet of pregnant bearded seals (Erignathus barbatus) during three spring breeding periods (2005, 2006 and 2007) with markedly contrasting ice conditions in Svalbard using stable isotopes (d13C and d15N) measured in whiskers collected from their newborn pups. The d15N values in the whiskers of individual seals ranged from 11.95 to 17.45 per mil, spanning almost 2 full trophic levels. Some seals were clearly dietary specialists, despite the species being characterised overall as a generalist predator. This may buffer bearded seal populations from the changes in prey distributions lower in the marine food web which seems to accompany continued changes in temperature and ice cover. Comparisons with isotopic signatures of known prey, suggested that benthic gastropods and decapods were the most common prey. Bayesian isotopic mixing models indicated that diet varied considerably among years. In the year with most fast-ice (2005), the seals had the greatest proportion of pelagic fish and lowest benthic invertebrate content, and during the year with the least ice (2006), the seals ate more benthic invertebrates and less pelagic fish. This suggests that the seals fed further offshore in years with greater ice cover, but moved in to the fjords when ice-cover was minimal, giving them access to different types of prey. Long-term trends of sea ice decline, earlier ice melt, and increased water temperatures in the Arctic are likely to have ecosystem-wide effects, including impacts on the forage bases of pagophilic seals.

Elements and isotopic measurements of magmatic rock samples from ODP Hole 104-642E

Trace element and isotopic signatures of magmatic rock samples from ODP Hole 642E at the Vøring Plateau provide insight into the interaction processes of mantle melt with crust during the initial magma extrusion phases at the onset of the continental breakup. The intermediate (basaltic-andesitic) to felsic (dacitic and rhyolitic) Lower Series magmas at ODP Hole 642E appear to be produced by large amounts of melting of upper crustal material. This study not only makes use of the traditional geochemical tools to investigate crust-mantle interaction, but also explores the value of Cs geochemistry as an additional tool. The element Cs forms the largest lithophile cation, and shows the largest contrast in concentration between (depleted) mantle and continental crust. As such it is a very sensitive indicator of involvement of crustal material. The Cs data reinforce the conclusion drawn from isotopic signatures that the felsic magmas are largely anatectic crustal melts. The down-hole geochemical variation within ODP Hole 642E defines a decreasing continental crustal influence from the Lower Series into the Upper Series. This is essential information to distinguish intrinsic geochemical properties of the mantle melts from signatures imposed by crustal contamination. A comparison with data from the SE Greenland margin highlights the compositional asymmetry of the crust-mantle interactions at both sides of the paleo-Iapetus suture. While Lower Series and Middle Series rocks from the SE Greenland margin have isotopic signatures reflecting interactions with lower and middle crust, such signatures have not been observed at the mid-Norwegian margin. The geochemical data either point to a dissimilar Caledonian crustal composition and/or to different geodynamic pre-breakup rifting history at the two NE Atlantic margin segments.

Isotopic composition of rocks from the Lau/Tonga back-arc basin, data of DSDP Leg 21 and ODP Legs 91 an 135

New trace element, Sr-, Nd-, Pb- and Hf isotope data provide insights into the evolution of the Tonga-Lau Basin subduction system. The involvement of two separate mantle domains, namely Pacific MORB mantle in the pre-rift and early stages of back-arc basin formation, and Indian MORB mantle in the later stages, is confirmed by these results. Contrary to models proposed in recent studies on the basis of Pb isotope and other compositional data, this change in mantle wedge character best explains the shift in the isotopic composition, particularly 143Nd/144Nd ratios, of modern Tofua Arc magmas relative to all other arc products from this region. Nevertheless, significant changes in the slab-derived flux during the evolution of the arc system are also required to explain second order variations in magma chemistry. In this region, the slab-derived flux is dominated by fluid; however, these fluids carry Pb with sediment-influenced isotopic signatures, indicating that their source is not restricted to the subducting altered mafic oceanic crust. This has been the case from the earliest magmatic activity in the arc (Eocene) until the present time, with the exception of two periods of magmatic activity recorded in samples from the Lau Islands. Both the Lau Volcanic Group, and Korobasaga Volcanic Group lavas preserve trace element and isotope evidence for a contribution from subducted sediment that was not transported as a fluid, but possibly in the form of a melt. This component shares similarities with that influencing the chemistry of the northern Tofua Arc magmas, suggesting some caution may be required in the adoption of constraints for the latter dependent upon the involvement of sediments from the Louisville Ridge. A key outcome of this study is to demonstrate that the models proposed to explain subduction zone magmatism cannot afford to ignore the small but important contributions made by the mantle wedge to the incompatible trace element inventory of arc magmas.

Geochemistry and isotopic composition of volcanic rocks of ODP Hole 128-794D

The Yamato Basin basement in the Sea of Japan was drilled below the sediment pile during Legs 127 and 128. Two superposed volcanic complexes are distinguished. The upper complex consists of continental tholeiite sills dated around 20-18 Ma and attributed to the rifting stage of the backarc basin. The lower complex consists of backarc basin basalts probably intruded below the upper complex during the spreading stage. Trace-element compositions and Sr and Nd isotopic signatures may be explained by mixing of at least two end members with a very small addition of crustal and subducted sediment component. Thus, upwelling of mantle diapir occurred during the rifting stage. Contribution of the depleted mantle increased in the spreading stage. The Neogene magmatic history of the Japan Sea is reviewed in the light of the ODP new data.

Abundance patterns and isotopic signals of morphotypes of Globigerinoides ruber

The chemical composition of shells of the planktonic foraminifer Globigerinoides ruber (white) is frequently used to determine past sea surface conditions. Recently, it has been shown that arbitrarily defined morphotypes within this species exhibit different chemical and isotopic signatures. Here, we investigate the occurrence through time and in space of morphological types of G. ruber (white) in late Quaternary and Holocene sediments of the central and the eastern Mediterranean Sea. In 115 samples representing two distinct time intervals (MIS 1-2 and MIS 9-12) at ODP Site 964 and the piston core GeoTü-SL96, we have defined three morphological types within this species and determined their relative abundances and stable isotopic composition. A quantitative analysis of morphological variation within G. ruber (white) in four samples revealed that the subjectively defined morphotypes occupy separate segments of a continuous and homogenous morphospace. We further show that the abundance of the morphotypes changes significantly between glacials and interglacials and that the three morphotypes of G. ruber show significant offsets in their stable isotopic composition. These offsets are consistent within glacial and interglacial stages but their sign is systematically reversed between the two Sites. Since the isotopic shifts among the three G. ruber morphotypes are systematic and often exceed 1per mil, their understanding is essential for the interpretation of all G. ruber-based proxy records for the paleoceanographic development of the Mediterranean during the late Quaternary.

Chemical and isotopic compositions of basaltic glasses and crusts from the Mid-Atlantic Ridge rift valley

Data presented in the paper suggest significant differences between thermodynamic conditions, under which magmatic complexes were formed in MAR at 29°-34°N and 12°-18°N. Melts occurring at 29°-34°N were derived by melting of a mantle source with homogeneous distribution of volatile components and arrived at the surface without significant fractionation, likely, due to their rapid ascent. The MAR segments between 12° and 18°N combine contrasting geodynamic environments of magmatism, which predetermined development of a large plume region with widespread mixing of melting products of geochemically distinct mantle sources. At the same time, this region is characterized by conditions favorable for origin of localized zones of anomalous plume magmatism. These sporadic magmatic sources were spatially restricted to MAR fragments with the Hess crust, whose compositional and mechanical properties were, perhaps, favorable for focusing and localization of plume magmatism. The plume source between 12° and 18°N beneath MAR may be geochemically heterogeneous.

Sr- and Nd-isotopic composition of bulk lithogenic sediments from the Eastern Mediterranean Sea (Table 1)

In order to characterize the provenance of lithogenic surface sediments from the Eastern Mediterranean Sea (EMS), residual (leached) fraction of 34 surface samples have been analysed for their 143Nd/144Nd and 87Sr/86Sr isotope ratios. The sample locations bracket all important entrances of riverine suspended matter into the EMS as well as all sub-basins of the EMS. The combined analyses of these two isotope ratios provide a precise characterization of the lithogenic fraction of surface sediments and record their dilution towards the central sub-basins. We reconstruct provenance and possible pathways of riverine dispersal and current redistribution, assuming more or less homogenous isotopic signatures and flux rates of the eolian fraction over the EMS. Lithogenic sediments entering the Ionian Sea from the Calabrian Arc and the Adriatic Sea are characterized by high 87Sr/86Sr isotope ratios and low epsilon-Nd(0) values (average 87Sr/86Sr=0.718005 and epsilon-Nd(0)=-11.06, n=5). Aegean Sea terrigenous sediments show an average ratio of 87Sr/86Sr=0.713089 (n=5) and values of epsilon-Nd(0)=-7.89 (n=5). The Aegean isotopic signature is traceable up to the southwest, south, and southeast of Crete. The sediment loads entering the EMS via the Aegean Sea are low and spread out mainly through the Strait of Casos (east of Crete). Surface sediments from the eastern Levantine Basin are marked by the highest epsilon-Nd(0) values (-3.3, n=6) and lowest 87Sr/86Sr isotope ratios (average 0.709541, n=6), reflecting the predominant input of the Nile sediment. The influence of the Nile sediment is traceable up to the NE-trending, eastern flank of the Mediterranean Ridge. The characterization of the modern riverine dispersal and eolian flux, based on isotope data, may serve as a tool to reconstruct climate-coupled variations of lithogenic sediment input into the EMS.

Radiogenic Hf isotopic composition of continental eolian dust in Pacific Ocean sediments

The inorganic silicate fraction extracted from bulk pelagic sediments from the North Pacific Ocean is eolian dust. It monitors the composition of continental crust exposed to erosion in Asia. 176Lu/177Hf ratios of modern dust are subchondritic between 0.011 and 0.016 but slightly elevated with respect to immature sediments. Modern dust samples display a large range in Hf isotopic composition (IC), -4.70 < epsilon-Hf < +16.45, which encompasses that observed for the time series of DSDP cores 885/886 and piston core LL44-GPC3 extending back to the late Cretaceous. Hafnium and neodymium isotopic results are consistent with a dominantly binary mixture of dust contributed from island arc volcanic material and dust from central Asia. The Hf-Nd isotopic correlation for all modern dust samples, epsilon-Hf= =0.78 epsilon-Nd = +5.66 (n =22, R**2 =0.79), is flatter than those reported so far for terrestrial reservoirs. Moreover, the variability in epsilon-Hf of Asian dust exceeds that predicted on the basis of corresponding epsilon-Nd values (34.76 epsilon-Hf < +2.5; -10.96< epsilon-Nd <-10.1). This is attributed to: (1) the fixing of an important unradiogenic fraction of Hf in zircons, balanced by radiogenic Hf that is mobile in the erosional cycle, (2) the elevated Lu/Hf ratio in chemical sediments which, given time, results in a Hf signature that is radiogenic compared with Hf expected from its corresponding Nd isotopic components, and (3) the possibility that diagenetic resetting of marine sediments may incorporate a significant radiogenic Hf component into diagenetically grown minerals such as illite. Together, these processes may explain the variability and more radiogenic character of Hf isotopes when compared to the Nd isotopic signatures of Asian dust. The Hf-Nd isotope time series of eolian dust are consistent with the results of modern dust except two samples that have extremely radiogenic Hf for their Nd (epsilon-Hf =+8.6 and +10.3, epsilon-Nd =39.5 and 39.8). These data may point to a source contribution of dust unresolved by Nd and Pb isotopes. The Hf IC of eolian dust input to the oceans may be more variable and more radiogenic than previously anticipated. The Hf signature of Pacific seawater, however, has varied little over the past 20 Myr, especially across the drastic increase of eolian dust flux from Asia around 3.5 Ma. Therefore, continental contributions to seawater Hf appear to be riverine rather than eolian. Current predictions regarding the relative proportions of source components to seawater Hf must account for the presence of a variable and radiogenic continental component. Data on the IC and flux of river-dissolved Hf to the oceans are urgently required to better estimate contributions to seawater Hf. This then would permit the use of Hf isotopes as a monitor of past changes in erosion.

(Table 1) Water column silicic acid concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Silicon isotopic signatures (d30Si) of water column silicic acid (Si(OH)4) were measured in the Southern Ocean, along a meridional transect from South Africa (Subtropical Zone) down to 57° S (northern Weddell Gyre). This provides the first reported data of a summer transect across the whole Antarctic Circumpolar Current (ACC). d30Si variations are large in the upper 1000 m, reflecting the effect of the silica pump superimposed upon meridional water transfer across the ACC: the transport of Antarctic surface waters northward by a net Ekman drift and their convergence and mixing with warmer upper-ocean Si-depleted waters to the north. Using Si isotopic signatures, we determine different mixing interfaces: the Antarctic Surface Water (AASW), the Antarctic Intermediate Water (AAIW), and thermoclines in the low latitude areas. The residual silicic acid concentrations of end-members control the d30Si alteration of the mixing products and with the exception of AASW, all mixing interfaces have a highly Si-depleted mixed layer end-member. These processes deplete the silicic acid AASW concentration northward, across the different interfaces, without significantly changing the AASW d30Si composition. By comparing our new results with a previous study in the Australian sector we show that during the circumpolar transport of the ACC eastward, the d30Si composition of the silicic acid pools is getting slightly, but significantly lighter from the Atlantic to the Australian sectors. This results either from the dissolution of biogenic silica in the deeper layers and/or from an isopycnal mixing with the deep water masses in the different oceanic basins: North Atlantic Deep Water in the Atlantic, and Indian Ocean deep water in the Indo-Australian sector. This isotopic trend is further transmitted to the subsurface waters, representing mixing interfaces between the surface and deeper layers. Through the use of d30Si constraints, net biogenic silica production (representative of annual export), at the Greenwich Meridian is estimated to be 5.2 ± 1.3 and 1.1 ± 0.3 mol Si/m**2 for the Antarctic Zone and Polar Front Zone, respectively. This is in good agreement with previous estimations. Furthermore, summertime Si-supply into the mixed layer of both zones, via vertical mixing, is estimated to be 1.6 ± 0.4 and 0.1 ± 0.5 mol Si/m**2, respectively.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Isotope ratios of basalts from ODP Leg 115 holes (Table 1)

Strontium, neodymium, and lead isotope ratios are reported for 13 Leg 115 basalts as well as 3 basalts from Texaco drill hole SM-1 on the Mascarene Plateau. The 87Sr/86Sr ratios and eNd range from 0.70330 to 0.70439 and 5.5 to 7.4, respectively, although 87Sr/86Sr ratios higher than 0.70383 are found only in SM-1 basalts. The high 87Sr/86Sr values are thought to reflect seawater Sr in secondary phases, although all samples were strongly leached in HC1 before analysis. 206Pb/204Pb ratios range from 18.53 to 18.80, and sho high 207Pb/204Pb and 208Pb/204Pb ratios relative to 206Pb/204Pb ratios, typical of Indian Ocean mid-ocean ridge (MORB) and oceanic-island basalts (OIB). Isotopic compositions of Leg 115 basalts generally fall between fields for MORB and Reunion Island basalts, consistent with the conclusion drawn from geochronological studies that Deccan flood basalt volcanism, the Chagos-Laccadive Ridge, and the Mascarene Plateau are all products of the Reunion mantle plume. Isotopic compositions of magmas produced by this plume have varied systematically with time in the direction of less "depleted," less MORB-like isotopic signatures. This compositional change has been accompanied by a decrease in eruption rate. We interpret Deccan volcanism as the voluminous beginning of the plume. Reduced entrainment of asthenosphere following melting of the plume head resulted in less MORB-like isotope ratios in magmas and a decrease in eruptive activity with time.