Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Chemistry of Jurassic/Cretaceous black shales

Black shale samples of Jurassic to Cretaceous age recovered during the 'Norwegian Shelf Drilling Program' between 1987 and 1991 from Sites 7430/10-U-01 (Barents Sea), 6814/04-U-02 (Norwegian Shelf near the Lofoten) and 6307/07-U-02 (Norwegian Shelf near Trondheim) were analyzed for major and trace elements. These laminated black shales are characterized by high total organic carbon (TOC) and total sulfur (TS) contents as well as by significant enrichments in several redox-sensitive and/or sulfide-forming trace metals (Ag, Bi, Cd, Co, Cr, Cu, Mo, Ni, Re, Sb, Tl, U, V, and Zn). Enrichment factors relative to 'average shale' are comparable to those found in Cenomanian-Turonian boundary event (CTBE) black shales and Mediterranean sapropels. The Re content is high in the studied black shales, with maximum values up to 1221 ng/g. Re/Mo ratios averaging 2.3*10**-3 are close to the seawater value. High trace metal enrichments and Re/Mo ratios close to the seawater value point to a dominantly anoxic and sulfidic water column during black shale formation. Interbeds with higher Re/Mo ratios, especially in high-resolution sampled core sections, point to brief periods of suboxic conditions. Additionally, enhanced Zn concentrations in the black shales from the Barents Sea support the assumption that hydrothermal activity was also high during black shale deposition. Trace metal signatures of black shales at different drill sites on a transect along the Norwegian Shelf are not only influenced by water depth but also by their location in the boreal realm. Metal enrichments are higher in the northern compared to the southern sites. Volgian (=Tithonian 151-144 Ma BP) black shales exhibit elevated trace metal contents in comparison to their Berriasian (144-137 Ma BP) counterparts. This probably reflects a change in the circulation pattern during periods of black shale formation. Therefore different paleoceanographic conditions, probably controlled by climatic change linked to the transgression of the paleo-sealevel and the North Atlantic opening, may have developed from the Volgian to the Berriasian.

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Dissolved chemical elements in river waters of the Wrangel Island

Pioneer information about chemical composition of river waters in the Wrangel Island has been obtained. It is shown that water composition reflects the lithogeochemical specifics of primary rocks and ore mineralization. In contrast to many areas of the Russian Far North river waters of the island are characterized by elevated background value of total mineralization (i.e., total dissolved solids, TDS) (0.3-2 g/l) and specific chemical type (SO4-Ca-Mg). This is related to abundance of Late Carboniferous gypsiferous and dolomitic sequences in the mountainous area of the island. It has also been established that salt composition of some streams is appreciably governed by supergene alterations of sulfide mineralization associated with quartz-carbonate vein systems. They make up natural centers of surface water contamination. Waters in such streams are characterized by low pH values (2.4-5.5), high TDS (up to 6-23 g/l) and SO4-Mg composition. These waters are also marked by anomalously high concentrations of heavy and non-ferrous metals, as well as REE, U, and Th.

Geochemistry at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Trace-element geochemistry of tholeiitic basalts from DSDP Hole 55-433C

Hole 433C, a multiple re-entry hole drilled in 1862 meters of water on Suiko Seamount in the central Emperor Seamounts, penetrated 387.5 meters of lava flows overlain by 163.0 meters of sediments. The recovered volcanic rocks consist of three flow units (1-3) of alkalic basalt underlain by more than 105 flows or flow lobes (Flow Units 4-67) of tholeiitic basalt. This study reports trace-element, including rare-earth element (REE), data for 25 samples from 24 of the least altered tholeiitic flows. These data are used to evaluate the origin and evolution of tholeiitic basalts from Suiko Seamount and to evaluate changes in the mantle source between the time when Suiko Seamount formed, 64.7 ± 1.1 m.y. ago (see Dalrymple et al., 1980), and the present day. Stearns (1946), Macdonald and Katsura (1964) and Macdonald (1968) have established that chemically distinct lavas erupt during four eruptive stages of development of a Hawaiian volcano. These stages, from initial to final, are shield-building, caldera-filling, post-caldera, and post-erosional. The lavas of the shield-building stage are tholeiitic basalts, which erupt rapidly and in great volume. The shield-building stage is quickly followed by caldera collapse and by the caldera-filling stage, during which the caldera is filled by tholeiitic and alkalic lavas. During the post-caldera stage, a relatively thin veneer of alkalic basalts and associated differentiated lavas are erupted, sometimes accompanied by minor eruptions of tholeiitic lava. After a period of volcanic quiescence and erosion, lavas of the nephelinitic suite, which include both alkalic basalts and strongly SiO2-undersaturated nephelinitic basalts, may erupt from satellite vents during the post-erosional stage. Many Hawaiian volcanoes develop through all four stages; but individual volcanoes have become extinct before the cycle is complete. We interpret the tholeiitic lavas drilled on Suiko Seamount to have erupted during either the shield-building or the caldera-filling stage, and the overlying alkalic flows to have erupted during either the caldera-filling or the post-caldera stage (see Kirkpatrick et al., 1980).

Chemical composition of bulk sediments from ODP Hole 199-1221C

A record of inorganic geochemical variability was produced from a contiguous sequence of 35 samples, with 1 cm spacing, recovered from Hole 1221C. This record covers from 153.91 to 154.27 meters below seafloor and spans the Carbon Isotope Excursion (CIE) associated with the Paleocene/Eocene boundary interval. Elemental concentrations were determined for Al, As, Ba, Ca, Fe, K, Mg, Mn, P, Si, Sr, Ti, Cd, Co, Cr, Cu, Hf, Mo, Nb, Ni, Pb, Pt, Re, Sc, V, Y, Zn, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Most concentration profiles exhibit a marked peak coincident with or just prior to the CIE. In addition, the rare earth element pattern exhibits a significant flattening of the typical, prominent negative Ce anomaly across the same interval.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Chemical composition of phosphorites, Fe-Mn nodules and crusts, and basalts from the West Pacific

The monograph gives the first systematic description of ore-bearing guyots from the West Pacific. It is mostly based on data obtained in numerous expeditions of Russian vessels during 1984-1992. Ore deposits located on upper parts of all slopes and tops of the guyots include phosphorites associated with cobalt- and platinum-rich ferromanganese crusts. Location, origin and prospecting of mineral deposits are discussed on the base of new data on metallogenic factors (geodynamics, tectonics, magmatism, sedimentation and morphostructures).