Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.

Clay mineral assemblages in the western Baltic Sea

Surface samples and nine cores from the western Baltic Sea and marginal water bodies were investigated for clay mineral composition. The clay mineral assemblages of recent sediments are rather homogeneous. Variations result mainly from the erosion of different glacial source deposits. High percentages of illite and low kaolinite/chlorite and quartz/feldspar ratios are characteristic for this glacial source. Advection of kaolinite-rich suspensions from the North Sea is believed to account for higher kaolinite/chlorite ratios in the Mecklenburg Bight. A contribution of the rivers Trave and Oder to the western Baltic Sea is indicated by increased smectite values in marginal water bodies. They correspond to increased kaolinite/chlorite and quartz/feldspar ratios. In the main basins the river signal is diluted beyond recognition. Cores from the Arkona, Bornholm and Gotland Basins penetrate through post-Littorina muds and sediments of the Ancylus Lake/Yoldia Sea into Late Glacial sediments of the Baltic Ice Lake. Clay mineral assemblages are characterized by an increase in kaolinite/chlorite ratios from Late Glacial to Holocene sediments, with a distinct shift at each facies change. This allows the distinction and core to core correlation of main lithological units with kaolinite/chlorite ratios. Kaolinite enrichment of Holocene muds corresponds to a brackish-marine facies and may reflect influx of kaolinite-rich suspensions from the North Sea. Cores from the lagoon of the Oderhaff show fluctuations in the contributions of the two main sediment sources: river suspension and glacial deposits during the Late Glacial and Postglacial sequence. Lacustrine sediments, which were deposited prior to 5500 years B.P. are characterized by smectite, kaolinite and quartz from the drainage area of the Oder river. Erosion of coastal and offshore glacial boulder clays with the Littorina transgression supplied a marine component rich in illite, chlorite and feldspars to the brackish muds of the Oderhaff.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

(Table 1) Insoluble aerosol concentrations and vertical fluxes at the eastern shelf of the Black Sea during breeze circulation in October 1987

Amounts of aerosols transported to the shelf surface were calculated on the basis of in situ measurements of concentrations of eolian matter (insoluble aerosol fraction) and vertical fluxes of settling dust in five areas of the Black Sea shelf from the Danube delta to the Inguri River mouth. More than 8.3 mln t of eolian matter are annually transported from the land over the shelf of the former USSR. At the same time more than 5.4 mln t are supplied to the northwestern shelf area, 1.7 mln t are supplied to the Crimean area, about 0.8 mln t are supplied to the Kerch-Taman' area, and about 0.45 mln t are supplied to the Caucasian area.

Megabenthic communities in the waters around Svalbard during POLARSTERN cruise ARK-VIII/2 (EPOS II)

Composition and distribution of megabenthic communities around Svalbard were investigated in June/July 1991 with 20 Agassiz trawl and 5 bottom trawl hauls in depths between 100 and 2100 m. About 370 species, ranging from sponges to fish, were identified in the catches. Species numbers per station ranged from 21 to 86. Brittle stars, such as Ophiacantha bidentata, Ophiura sarsi and Ophiocten sericeum, were most important in terms of constancy and relative abundance in the catches. Other prominent faunal elements were eunephthyid alcyonarians, bivalves, shrimps, sea stars and fish (Gadidae, Zoarcidae, Cottidae). Multivariate analyses of the species and environmental data sets showed that the spatial distribution of the megabenthos was characterized by a pronounced depth zonation: abyssal, bathyal, off-shore shelf and fjordic communities were discriminated. However, a gradient in sediment properties, especially the organic carbon content, seemed to superimpose on the bathymetric pattern. Both main factors are interpreted as proxies of the average food availability, which is, hence, suggested to have the strongest influence in structuring megabenthic communities off Svalbard.

Mineralogical and geochemical data from five lake sediment cores of Lake Donggi Cona

Sediments of Lake Donggi Cona on the northeastern Tibetan Plateau were studied to infer changes in the lacustrine depositional environment, related to climatic and non-climatic changes during the last 19 kyr. The lake today fills a 30 X 8 km big and 95 m deep tectonic basin, associated with the Kunlun Fault. The study was conducted on a sediment-core transect through the lake basin, in order to gain a complete picture of spatiotemporal environmental change. The recovered sediments are partly finely laminated and are composed of calcareous muds with variable amounts of carbonate micrite, organic matter, detrital silt and clay. On the basis of sedimentological, geochemical, and mineralogical data up to five lithological units (LU) can be distinguished that document distinct stages in the development of the lake system. The onset of the lowermost LU with lacustrine muds above basal sands indicates that lake level was at least 39 m below the present level and started to rise after 19 ka, possibly in response to regional deglaciation. At this time, the lacustrine environment was characterized by detrital sediment influx and the deposition of siliciclastic sediment. In two sediment cores, upward grain-size coarsening documents a lake-level fall after 13 cal ka BP, possibly associated with the late-glacial Younger Dryas stadial. From 11.5 to 4.3 cal ka BP, grainsize fining in sediment cores from the profundal coring sites and the onset of lacustrine deposition at a litoral core site (2m water depth) in a recent marginal bay of Donggi Cona document lake-level rise during the early tomid-Holocene to at least modern level. In addition, high biological productivity and pronounced precipitation of carbonate micrites are consistent with warm and moist climate conditions related to an enhanced influence of summer monsoon. At 4.3 cal ka BP the lake system shifted from an aragonite- to a calcite-dominated system, indicating a change towards a fully open hydrological lake system. The younger clay-rich sediments are moreover non-laminated and lack any diagenetic sulphides, pointing to fully ventilated conditions, and the prevailing absence of lake stratification. This turning point in lake history could imply either a threshold response to insolation-forced climate cooling or a response to a non-climatic trigger, such as an erosional event or a tectonic pulse that induced a strong earthquake, which is difficult to decide from our data base.

A four-year record of UK'37- and TEX86-derived sea surface temperature estimates from sinking particles in the filamentous upwelling region off Cape Blanc, Mauritania

Lipid biomarker records from sinking particles collected by sediment traps are excellent tools to study the seasonality of biomarker production as well as processes of particle formation and settling, ultimately leading to the preservation of the biomarkers in sediments. Here we present records of the biomarker indices UK'37 based on alkenones and TEX86 based on isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), both used for the reconstruction of sea surface temperatures (SST). These records were obtained from sinking particles collected using a sediment trap moored in the filamentous upwelling zone off Cape Blanc, Mauritania, at approximately 1300 water depth during a four-year time interval between 2003 and 2007. Mass and lipid fluxes are highest during peak upwelling periods between October and June. The alkenone and GDGT records both display pronounced seasonal variability. Sinking velocities calculated from the time lag between measured SST maxima and minima and corresponding index maxima and minima in the trap samples are higher for particles containing alkenones (14-59 m/d) than for GDGTs (9-17 m/d). It is suggested that GDGTs are predominantly exported from shallow waters by incorporation in opal-rich particles. SST estimates based on the UK'37 index faithfully record observed fluctuations in SST during the study period. Temperature estimates based on TEX86 show smaller seasonal amplitudes, which can be explained with either predominant production of GDGTs during the warm season, or a contribution of GDGTs exported from deep waters carrying GDGTs in a distribution that translates to a high TEX86 signal.

(Table 3) Stable isotope composition of sof t tissues of specimens from the Sea of Okhotsk

We discovered and investigated several cold-seep sites in four depth zones of the Sea of Okhotsk off Northeast Sakhalin: outer shelf (160-250 m), upper slope (250-450 m), intermediate slope (450-800 m), and Derugin Basin (1450-1600 m). Active seepage of free methane or methane-rich fluids was detected in each zone. However, seabed photography and sampling revealed that the number of chemoautotrophic species decreases dramatically with decreasing water depth. At greatest depths in the Derugin Basin, the seeps were inhabited by bacterial mats and bivalves of the families Vesicomyidae (Calyptogena aff. pacifica, C. rectimargo, Archivesica sp.), Solemyidae (Acharax sp.) and Thyasiridae (Conchocele bisecta). In addition, pogonophoran tubeworms of the family Sclerolinidae were found in barite edifices. At the shallowest sites, on the shelf at 160 m, the seeps lack chemoautotrophic macrofauna; their locations were indicated only by the patchy occurrence of bacterial mats. Typical seep-endemic metazoans with chemosynthetic symbionts were confined to seep sites at depths below 370 m. A comparative analysis of the structure of seep and background communities suggests that differences in predation pressure may be an important determinant of this pattern. The abundance of predators such as carnivorous brachyurans and asteroids, which can invade seeps from adjacent habitats and efficiently prey on sessile seep bivalves, decreased very pronouncedly with depth. We conclude from the obvious correlation with the conspicuous pattern in the distribution of seep assemblages that, on the shelf and at the upper slope, predator pressure may be high enough to effectively impede any successful settlement of viable populations of seep-endemic metazoans. However, there was also evidence that other depth-related factors, such as bottom-water current, sedimentary regimes, oxygen concentrations and the supply of suitable settling substrates, may additionally regulate the distribution of seep fauna in the area. As a consequence of the pronounced pattern in the distribution of seep communities, their ecological significance as food sources of surrounding background fauna increased with water depth. Isotopic analyses suggest that in the Derugin Basin seep colonists feed on chemoautotrophic seep organisms, either directly or by preying on metazoans with chemosynthetic symbionts. In contrast, seep organisms apparently do not contribute to the nutrition of the adjacent background fauna on the shelf and at the slope. In this area, elevated epifaunal abundances at seep sites were caused primarily by the availability of suitable settling substrates rather than by an enrichment of food supply.

Sedimentology of ODP Leg 119 samples

Cretaceous to Quaternary sediments recovered at Leg 119 Sites 738 and 744 on the southern tip of the Kerguelen Plateau were studied in order to determine the depositional environment and the paleoceanography of the southern Indian Ocean and especially the long-term glacial history of East Antarctica. Emphasis is given to bulk-sediment composition, grain-size data, and clay mineralogy. The sediment sequence at the two sites is generally of a highly pelagic character, with nannofossil oozes, chalks, and limestones dominant from the Turanian to upper Miocene and diatom oozes dominant within the uppermost Miocene to Holocene interval. The first indication of glaciation at sea level is the occurrence of isolated gravel and terrigenous sand grains, which indicate ice rafting in the middle Eocene interval of 45.0-42.3 Ma. A major intensification of glaciation, probably the onset of continental East Antarctic glaciation, is recorded in sediments of early Oligocene age (36.0 Ma). All major sediment parameters document this event. The clay mineralogy changes from smectite-dominated assemblages, typical of moderately warm and humid climatic conditions in which chemical weathering processes are prevalent, to illite- and chlorite-dominated assemblages, indicative of cooler climates and physical weathering. Ice-rafted debris of both gravel and sand size occurs in large quantities in that interval and coincides with a change in the mode of carbonate deposition. Carbonate contents are relatively high and uniform (90%-95%) in strata younger than early Oligocene; in Oligocene to upper Miocene strata they fluctuate between 65% and 95%. Oligocene and Neogene hiatuses reflect an intensification of oceanic circulation and the increased erosional force of Circumpolar Deep Water. The long-term Cenozoic cooling trend was interrupted by a phase of early Miocene warming indicated by maximum Neogene smectite concentrations. Although ice-rafted debris is present only in minor amounts and mainly in the silt fraction of early Oligocene to late Miocene age, it shows that glaciers advanced to the East Antarctic shoreline throughout that time. Ice-rafting activity drastically increased in latest Miocene time, when carbonate deposition decreased and diatom ooze sedimentation started. This suggests a pronounced intensification of Antarctic glaciation combined with a northward migration of the Polar Front.

Planktonic foraminifera fluxes and stable isotope ratios in the Irminger Sea

Past water column stratification can be assessed through comparison of the d18O of different planktonic foraminiferal species. The underlying assumption is that different species form their shells simultaneously, but at different depths in the water column. We evaluate this assumption using a sediment trap time-series of Neogloboquadrina pachyderma (s) and Globigerina bulloides from the NW North Atlantic. We determined fluxes, d18O and d13C of shells from two size fractions to assess size-related effects on shell chemistry and to better constrain the underlying causes of isotopic differences between foraminifera in deep-sea sediments. Our data indicate that in the subpolar North Atlantic differences in the seasonality of the shell flux, and not in depth habitat or test size, determine the interspecies Delta d18O. N. pachyderma (s) preferentially forms from early spring to late summer, whereas the flux ofG. bulloides peaks later in the season and is sustained until autumn. Likewise, seasonality influences large and small specimens differently, with large shells settling earlier in the season. The similarity of the seasonal d18O patterns between the two species indicates that they calcify in an overlapping depth zone close to the surface. However, their d13C patterns are markedly different (>1 per mil). Both species have a seasonally variable offset from d13CDIC that appears to be governed primarily by temperature, with larger offsets associated with higher temperatures. The variable offset from d13CDIC implies that seasonality of the flux affects the fossil d13C signal, which has implications for reconstruction of the past oceanic carbon cycle.

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

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.

Geochemical data and mineralogical properties of bulk sediment composition of ODP Hole 195-1202B

During Leg 195 of the Ocean Drilling Program, Site 1202 was drilled in the subtropical northwestern Pacific Ocean beneath the Kuroshio (Black Current) between northern Taiwan and the Ryukyu Island Arc on the northern flank of the I-Lan Ridge at 1274 m water depth. The upper 110 m of the Site 1202 section, composed of dark grey calcareous silty clay, provide an expanded record of environmental changes during the last 28 kyr. The sediments were deposited at high sedimentation rates between 3.0 and 5.0 m/kyr and peak values of 9.0 m/kyr between 15.1 and 11.2 ka BP. Variations in the modes and sources of detrital sediment input, as inferred from sediment granulometry, mineralogy, and elemental XRF-scanner data, reflect changes in environmental boundary conditions related to sea-level changes, Kuroshio variability, and the climate-driven modes of fluvial runoff. The provenance data point to increased sediment supply from northwestern Taiwan between 28 and 19.5 ka BP and from East China sources between 19.5 and 11.2 ka BP. The change in provenance at 19.5 ka BP reflects increased fluvial runoff from the Yangtze River and strong sediment reworking from the East China Sea shelf in the course of increased humidity and postglacial sea-level rise, particularly after 15.1 ka BP. The Holocene was dominated by sediments that originated from rivers in northeastern Taiwan. For the pre-Holocene period prior to 11.2 ka BP, low portions of sortable silt (63-10 ?m) show that the Kuroshio did not enter the Okinawa Trough, because of low sea-level. In turn, high proportions of sortable silt and sediment provenance from northeastern Taiwan point to strong ocean circulation under the direct and persistent influence of the Kuroshio during the Holocene. The reentrance of the Kuroshio to the Okinawa Trough was heralded by two pulses in relative current strengthening at 11.2 and 9.5 ka BP, as documented by stepwise increases in sortable silt in the lower Holocene section. From a global perspective, environmental changes in the southern Okinawa Trough show affinities to climate change in the western Pacific warm pool with little influence of climate teleconnections from the North Atlantic realm, otherwise seen in many other marine and terrestrial palaeoclimate records from southeastern Asia.