Ice characteristics, and mercury content of ice, air and underlying seawater in the eastern Beaufort Sea

The Arctic sea-ice environment has been undergoing dramatic changes in the past decades; to which extent this will affect the deposition, fate, and effects of chemical contaminants remains virtually unknown. Here, we report the first study on the distribution and transport of mercury (Hg) across the ocean-sea-ice-atmosphere interface in the Southern Beaufort Sea of the Arctic Ocean. Despite being sampled at different sites under various atmospheric and snow cover conditions, Hg concentrations in first-year ice cores were generally low and varied within a remarkably narrow range (0.5-4 ng/L), with the highest concentration always in the surface granular ice layer which is characterized by enriched particle and brine pocket concentration. Atmospheric Hg depletion events appeared not to be an important factor in determining Hg concentrations in sea ice except for frost flowers and in the melt season when snowpack Hg leaches into the sea ice. The multiyear ice core showed a unique cyclic feature in the Hg profile with multiple peaks potentially corresponding to each ice growing/melting season. The highest Hg concentrations (up to 70 ng/L) were found in sea-ice brine and decrease as the melt season progresses. As brine is the primary habitat for microbial communities responsible for sustaining the food web in the Arctic Ocean, the high and seasonally changing Hg concentrations in brine and its potential transformation may have a major impact on Hg uptake in Arctic marine ecosystems under a changing climate.

Water chemistry and heat budget of the Churchill River estuary region

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April-May. In the Churchill Estuary, conditions varied abruptly throughout winter-spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (~6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter-spring transition, which implies sensitivity to climate change.

Southern Ocean CO2 uptake and buffer factor from model run 2012-2100, with links to model results

The Southern Ocean is a key region for global carbon uptake and is characterised by a strong seasonality with the annual CO2 uptake being mediated by biological carbon draw-down in summer. Here, we show that the contribution of biology to CO2 uptake will become even more important until 2100. This is the case even if biological production remains unaltered and can be explained by the decreasing buffer capacity of the ocean as its carbon content increases. The same amount of biological carbon draw-down leads to a more than twice as large reduction in CO2 (aq) concentration and hence to a larger CO2 gradient between ocean and atmosphere that drives the gas-exchange. While the winter uptake south of 44°S changes little, the summer uptake increases largely and is responsible for the annual mean response. The combination of decreasing buffer capacity and strong seasonality of biological carbon draw-down introduces a strong and increasing seasonality in the anthropogenic carbon uptake.

Three species distribution models for the marine diatom Fragilariopsis kerguelensis of the Southern Ocean, links to NetCDF files

Fragilariopsis kerguelensis, a dominant diatom species throughout the Antarctic Circumpolar Current, is coined to be one of the main drivers of the biological silicate pump. Here, we study the distribution of this important species and expected consequences of climate change upon it, using correlative species distribution modeling and publicly available presence-only data. As experience with SDM is scarce for marine phytoplankton, this also serves as a pilot study for this organism group. We used the maximum entropy method to calculate distribution models for the diatom F. kerguelensis based on yearly and monthly environmental data (sea surface temperature, salinity, nitrate and silicate concentrations). Observation data were harvested from GBIF and the Global Diatom Database, and for further analyses also from the Hustedt Diatom Collection (BRM). The models were projected on current yearly and seasonal environmental data to study current distribution and its seasonality. Furthermore, we projected the seasonal model on future environmental data obtained from climate models for the year 2100. Projected on current yearly averaged environmental data, all models showed similar distribution patterns for F. kerguelensis. The monthly model showed seasonality, for example, a shift of the southern distribution boundary toward the north in the winter. Projections on future scenarios resulted in a moderately to negligibly shrinking distribution area and a change in seasonality. We found a substantial bias in the publicly available observation datasets, which could be reduced by additional observation records we obtained from the Hustedt Diatom Collection. Present-day distribution patterns inferred from the models coincided well with background knowledge and previous reports about F. kerguelensis distribution, showing that maximum entropy-based distribution models are suitable to map distribution patterns for oceanic planktonic organisms. Our scenario projections indicate moderate effects of climate change upon the biogeography of F. kerguelensis.

Strontium isotopes, ages and carbonate content of sediments from the Agulhas Current

The Agulhas Leakage represents a significant portion of the warm, surface return flow of the global overturning circulation and thus may be an important feedback in the ocean climate system. Models indicate that reduced leakage could be caused by a stronger Agulhas Current and/or a more upstream (eastward) Agulhas Retroflection, while a weaker Agulhas Current would result in a more westward retroflection and increased leakage. However, data for the Last Glacial Maximum support both a weaker Agulhas Current and less leakage, implying a possible displacement of the retroflection. We present new 87Sr/86Sr results for modern sediments within this region, confirming that the modern pathway of the Agulhas Current, Retroflection, and Leakage can be traced by terrigenous sediment provenance using Sr isotopes. New 87Sr/86Sr data from sediments deposited during the Last Glacial Maximum suggest that the glacial Agulhas Current and Retroflection followed nearly their modern trajectory. The provenance data appear to rule out both a stronger Agulhas Current and a more upstream Agulhas Retroflection. We conclude that the reduced glacial leakage was caused by the weakened Agulhas Current, with no significant change in the retroflection position. This is inconsistent with the model predictions and thus emphasizes the need for further work in this region.

Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.

Pore water isotopic ratios of CO2 and SO4, and sediment CH4 content of ODP Leg 164 sites

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The d13C values of dissolved CO2 (sum CO2) are as 13C-depleted as -37.7 per mil PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using a two-component mixing model suggests that ~24% of the carbon residing in the sum CO2 pool is derived from biogenic methane. Independent diagenetic modeling of a methane concentration profile (Site 995) indicates that peak methane oxidation rates approach 0.005 µmol/cm**3/yr, and that anaerobic methane oxidation is responsible for consuming ~35% of the total sulfate flux into the sediments. Thus, anaerobic methane oxidation is a significant biogeochemical sink for sulfate, and must affect interstitial sulfate concentrations and sulfate gradients. Such high proportions of sulfate depletion because of anaerobic methane oxidation are largely undocumented in continental rise sediments with overlying oxic bottom waters. We infer that the additional amount of sulfate depleted through anaerobic methane oxidation, fueled by methane flux from below, causes steeper sulfate gradients above methane-rich sediments. Similar pore water chemistries should occur at other methane-rich, continental-rise settings associated with gas hydrates.

Cation exchange capacity and water content of ODP sites from Nankai

Pore fluid chlorinity lower than seawater is often observed in accretionary wedges and one of the possible causes of pore water freshening is the smectite to illite reaction. This reaction occurs during diagenesis in the 80-150°C temperature range. Low chlorinity anomalies observed at the toe of accretionary wedges have thus been interpreted as evidence for lateral fluid migration from inner parts of the wedge and the seismogenic zone. However, temperature conditions in Nankai Trough are locally high enough for the smectite to illite transition to occur in situ. Cation exchange capacity is here used as a proxy for smectite content in the sediment and the amount of interlayer water released during the smectite to illite reaction represents in average 12 water molecules per cation charge. Water and chloride budget calculations show that there is enough smectite to explain the chlorinity anomalies by in situ reactions. The shape of the pore fluid chlorinity profiles can be explained if compaction is also taken into account in the model. Lateral flow is not needed. This argument, based solely on chloride concentration, does not imply that lateral flow is absent. However, previous estimations of lateral fluid fluxes, and of the duration of transient flow events along the de.collement, should be reconsidered.

Sediment facies of the Indian-Pakistan continental margin, Indian Ocean Expedition

The studies described here base mainly on sedimentary material collected during the "Indian Ocean Expedition" of the German research vessel "Meteor" in the region of the Indian-Pakistan continental margin in February and March 1965. Moreover,samples from the mouth of the Indus-River were available, which were collected by the Pakistan fishing vessel "Machhera" in March 1965. Altogether, the following quantities of sedimentary material were collected: 59.73 m piston cores. 54.52 m gravity cores. 33 box grab samples. 68 bottom grab samples Component analyses of the coarse fraction were made of these samples and the sedimentary fabric was examined. Moreover, the CaCO3 and Corg contents were discussed. From these investigations the following history of sedimentation can be derived: Recent sedimentation on the shelf is mainly characterized by hydrodynamic processes and terrigenous supply of material. In the shallow water wave action and currents running parallel to the coast, imply a repeated reworking which induces a sorting of the grains and layering of the sediments as well as a lack of bioturbation. The sedimentation rate is very high here. From the coast-line down to appr. 50 m the sediment becomes progressively finer, the conditions of deposition become less turbulent. On the outer shelf the sediment is again considerably coarser. It contains many relicts of planktonic organisms and it shows traces of burrowing. Indications for redeposition are nearly missing, a considerable part of the fine fraction of the sediments is, however, whirled up and carried away. In wide areas of the outer shelf this stirring has gained such a degree that recent deposits are nearly completely missing. Here, coarse relict sands rich in ooids are exposed, which were formed in very shallow stirred water during the time when the sea reached its lowest level, i.e. at the turn of the Pleistocene to the Holocene. Below the relict sand white, very fine-grained aragonite mud was found at one location (core 228). This aragonite mud was obviously deposited in very calm water of some greater depth, possibly behind a reef barrier. Biochemic carbonate precipitation played an important part in the formation of relict sands and aragonite muds. In postglacial times the relict sands were exposed for long periods to violent wave action and to areal erosion. In the present days they are gradually covered by recent sediments proceeding from the sides. On the continental margin beyond the shelf edge the distribution of the sediments is to a considerable extent determined by the morphology of the sea bottom. The material originating from the continent and/or the shelf, is less transported by action of the water than by the force of gravity. Within the range of the uppermost part of the continental slope recent sedimentation reaches its maximum. Here the fine material is deposited which has been whirled up in the zone of the relict sands. A laminated fine-grained sediment is formed here due to the very high sedimentation rate as well as to the extremely low O2-content in the bottom water, which prevents life on the bottom of the sea and impedes thus also bioturbation. The lamination probaly reflects annual variation in deposition and can be attributed to the rhythm of the monsoon with its effects on the water and the weather conditions. In the lower part of the upper continental slope sediments are to be found which show in varying intensity, intercalations of fine material (silt) from the shelf, in large sections of the core. These fine intercalations of allochthonous material are closely related to the autochthonous normal sediment, so that a great number of small individual depositional processes can be inferred. In general the intercalations are missing in the uppermost part of the cores; in the lower part they can be met in different quantities, and they reach their maximum frequency in the upper part of the lower core section. The depositions described here were designated as turbid layer sediments, since they get their material from turbid layers, which transport components to the continental slope which have been whirled up from the shelf. Turbidites are missing in this zone. Since the whole upper continental slope shows a low oxygen-content of the bottom water the structure of the turbid layer sediments is more or less preserved. The lenticular-phacoidal fine structure does, however, not reflect annual rhythms, but sporadic individual events, as e.g. tsunamis. At the lower part of the continental slope and on the continental rise the majority of turbidites was deposited, which, during glacial times and particularly at the beginning of the post-glacial period, transported material from the zone of relict sands. The Laccadive Ridge represented a natural obstacle for the transport of suspended sediments into the deep sea. Core SIC-181 from the Arabian Basin shows some intercalations of turbidites; their material, however, does not originate from the Indian Shelf, but from the Laccadive Ridge. Within the range of the Indus Cone it is surprising that distinct turbidites are nearly completely missing; on the other hand, turbid layer sediments are to be found. The bottom of the sea is showing still a slight slope here, so that the turbidites funneled through the Canyon of the Swatch probably rush down to greater water depths. Due to the particularly large supply of suspended material by theIndus River the turbid layer sediments show farther extension than in other regions. In general the terrigenous components are concentrated on the Indus Cone. It is within the range of the lower continental slope that the only discovery of a sliding mass (core 186) has been located. It can be assumed that this was set in motion during the Holocene. During the period of time discussed here the following development of kind and intensity of the deposition of allochthonous material can be observed on the Indian-Pakistan continental margin: At the time of the lowest sea level the shelf was only very narrow, and the zone in which bottom currents were able to stir up material by oscillating motion, was considerably confined. The rivers flowed into the sea near to the edge of the shelf. For this reason the percentage of terrigenous material, quartz and mica is higher in the lower part of many cores (e.g. cores 210 and 219) than in the upper part. The transition from glacial to postglacial times caused a series of environmental changes. Among them the rise of the sea level (in the area of investigation appr. 150 m) had the most important influence on the sedimentation process. In connection with this event many river valleys became canyons, which sucked sedimentary material away from the shelf and transported it in form of turbidites into the deep sea. During the rise of the sea level a situation can be expected with a maximum area of the comparatively plane shelf being exposed to wave action. During this time the process of stirring up of sediments and formation of turbid layers will reach a maximum. Accordingly, the formation of turbidites and turbid layer sediments are most frequent at the same time. This happened in general in the older polstglacial period. The present day high water level results in a reduced supply of sediments into the canyons. The stirring up of sediments from the shelf by wave action is restricted to the finest material. The missing of shelf material in the uppermost core sections can thus be explained. The laminated muds reflect these calm sedimentation conditions as well. In the southwestern part of the area of investigation fine volcanic glass was blown in during the Pleistocene, probably from the southeast. It has thus become possible to correlate the cores 181, 182, 202. Eolian dust from the Indian subcontinent represents probably an important component of the deep sea sediments. The chemism of the bottom as well as of the pore water has a considerable influence on the development of the sediments. Of particular importance in this connection is a layer with a minimum content of oxygen in the sea water (200-1500 m), which today touches the upper part of the continental slope. Above and beyond this oxygen minimum layer somewhat higher O2-values are to be observed at the sea bottom. During the Pleistocene the oxygen minimum layer has obviously been locatedin greater depth as is indicated by the facies of laminated mud occuring in the lower part of core 219. The type of bioturbation is mainly determined by the chemism. Moreover, the chemism is responsible for a considerable selective dissolution, either complete or partial, of the sedimentary components. Within the range of the oxygen minimum layer an alkaline milieu is developed at the bottom. This causes a complete or partial dissolution of the siliceous organisms. Here, bioturbation is in general completely missing; sometimes small pyrite-filled burrowing racks are found. In the areas rich in O2 high pH-values result in a partial dissolution of the calcareous shells. Large, non-pyritized burrowing tracks characterize the type of bioturbation in this environment. A study of the "lebensspuren" in the cores supports the assumption that, particularly within the region of the Laccadive Basin, the oxygen content in the bottom sediments was lower than during the Holocene. This may be attributed to a high sedimentation rate and to a lower O2-content of the bottom water. The composition of the allochthonous sedimentary components, detritus and/or volcanic glass may locally change the chemism to a considerable extent for a certain time; under such special circumstances the type of bioturbation and the state of preservation of the components may be different from those of the normal sediment.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

Heat flow ratios of stations from the Iberian abyssal plain (Table 1)

New heat flow observations have been made in the Iberia abyssal plain off the Galicia margin along the transeat of Ocean Drilling Program Leg 149 drill sites. in order to investigate the nature of this unusually wide and deep continet-ocean transition region. Our results indicate the presence of three separate zones. Average values of 47.5 +/- 3 mW/m in the westernmost zone III agree with predictions of standard oceanic lithospheric models for its estimated age of 126 Ma. In contrast, the heat flow within zone II is 5-15 mW/m higher than predicted. assuming that the mantle heat flow remains constant across the basin. This region of high values is coincident with the location of a major intra-crustal "S"-type reflector east of ODP Site 900. and the anomaly is consistent with the presence of 2-3 km of primarily upper continental crust above the reflector, with concentrations of radiogenic components similar to those from granodiorite samplles dredged off Galicia Bank. It is not, however, consistent with the low values of heat production measured on gabbroic sanhples from its western end at ODP Site 900. In zone I, detailed measurements across the tilted fault block south of ODP Site 901 show consistent variations which closely match predictions due to the effects of basement structure and sediment deposition. There is no evidence for variations due to vertical convective transport along the dipping basement fault block. Once corrected for these variations. measurements in zone I yield average values that agree quite well with previous measurements across Calicia Bank. indicating no systematic landward increase in heat flow with decreasing amounts of continental, extension.