Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.

Sediment composition in NE Greenland Fjords, Shelf, and Slope

In order to document changes in Holocene glacier extent and activity in NE Greenland (~73° N) we study marine sediment records that extend from the fjords (PS2631 and PS2640), across the shelf (PS2623 and PS2641), to the Greenland Sea (JM07-174GC). The primary bedrock geology of the source areas is the Caledonian sediment outcrop, including Devonian red beds, plus early Neoproterozoic gneisses and early Tertiary volcanics. We examine the variations in colour (CIE*), grain size, and bulk mineralogy (from X-ray diffraction of the <2 mm sediment fraction). Fjord core PS2640 in Sofia Sund, with a marked red hue, is distinct in grain size, colour and mineralogy from the other fjord and shelf cores. Five distinct grain-size modes are distinguished of which only one is associated with a coarse ice-rafting signal - this mode is rare in the mid- and late Holocene. A sediment unmixing program (SedUnMixMC) is used to characterize down-core changes in sediment composition based on the upper late Holocene sediments from cores PS2640 (Sofia Sund), PS2631 (Kaiser Franz Joseph Fjord) and PS2623 (south of Shannon Is), and surface samples from the Kara Sea (as an indicator of transport from the Russian Arctic shelves). Major changes in mineral composition are noted in all cores with possible coeval shifts centred c. 2.5, 4.5 and 7.5 cal. ka BP (±0.5 ka) but are rarely linked with changes in the grain-size spectra. Coarse IRD (>2 mm) and IRD-grain-size spectra are rare in the last 9-10 cal. ka BP and, in contrast with areas farther south (~68° N), there is no distinct IRD signal at the onset of neoglaciation. Our paper demonstrates the importance of the quantitative analysis of sediment properties in clarifying source to sink changes in glacial marine environments.

Physical properties, grain size distribution and clay mineralogy of ODP Leg 117 sites

The fabric of sediments recovered at sites drilled on the Indus Fan, Owen Ridge, and Oman margin during Ocean Drilling Program Leg 117 was examined by scanning electron microscopy to document changes that accompany sediment burial. Two sediment types were studied: (1) biogenic sediments consisting of a variety of marly nannofossil and nannofossil oozes and chalks and (2) terrigenous sediments consisting of fine-grained turbidites deposited in association with the Indus Fan. Biogenic sediments were examined with samples from the seafloor to depths of 306 m below seafloor (mbsf) on the Owen Ridge (Site 722) and 368 mbsf on the Oman margin (Sites 723 and 728). Over these depth ranges the biogenic sediments are characterized by a random arrangement of microfossils and display little chemical diagenetic alteration. The microfossils are dispersed within a fine-grained matrix that is predominantly microcrystalline carbonate particles on the Owen Ridge and clay and organic matter on the Oman margin. Sediments with abundant siliceous microfossils display distinct, open fabrics with high porosity. Porosity reduction resulting from gravitational compaction appears to be the primary process affecting fabric change in the biogenic sediment sections. Fabric of illite-rich clayey silts and silty claystones from the Indus Fan (Site 720) and Owen Ridge (Sites 722 and 731) was examined for a composite section extending from 45 to 985 mbsf. In this section fabric of the fine-grained turbidites changes from one with small flocculated clay domains, random particle arrangement, and high porosity to a fabric with larger domains, strong preferred particle orientation roughly parallel to bedding, and lower porosity. These changes are accomplished by a growth in domain size, primarily through increasing face-to-face contacts, and by particle reorientation which is characterized by a sharp increase in alignment with bedding between 200 and 400 mbsf. Despite extensive particle reorientation, flocculated clay fabric persists in the deepest samples examined, particularly adjacent to silt grains, and the sediments lack fissility. Fabric changes over the 45-985 mbsf interval occur in response to gravitational compaction. Porosity reduction and development of preferred particle orientation in the Indus Fan and Owen Ridge sections occur at greater depths than outlined in previous fabric models for terrigenous sediments as a consequence of a greater abundance of silt and a greater abundance of illite and chlorite clays.

Mineralogy and geochemistry of altered ash, pelagic clay, and a clay vein in basalt from DSDP Leg 62 Holes

Volcanic ash was recovered from lower Aptian to Albian deposits from DSDP Sites 463, 465, and 466; pelagic clay of the upper Pleistocene to Upper Cretaceous was recovered mainly from Site 464, with minor amounts at Sites 465 and 466. We present X-ray-mineralogy data on pelagic clay and altered volcanic ash recovered from the four Leg 62 sites. In addition, two ash samples from Sites 463 and 465, a pelagic clay from Site 464, and a clay vein from the basaltic basement at Site 464 each were analyzed for major, minor, and trace elements. Our purpose is to describe the mineralogy and chemistry of altered ash and pelagic clays, to determine the sources of their parent material, and to delineate the diagenetic history of these clay-rich deposits. Correlation of chemistry and mineralogy of ash and pelagic clay with volcanic rocks suspected to be their parent material is not always straightforward, because weathering and diagenetic alteration caused depletion or enrichment of many elements.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Organic geochemistry and sedimentology of lower to mid-Cretaceous at DSDP Leg 77 Holes

Analyses of 40 carbonate core samples - 27 from Site 535, 12 from Site 540, and 1 from Site 538A - have confirmed many of the findings of the Shipboard Scientific Party. The samples, all but one Early to mid-Cretaceous in age (Berriasian to Cenomanian), reflect sequences of cyclically anoxic and oxic depositional environments. They are moderately to very dark colored, dominantly planar-parallel, laminated lime mudstones. Most show the effects of intense mechanical compaction. Visual kerogen characteristics and conventional Rock-Eval parameters indicate that these deep basinal carbonates contain varying mixtures of thermally immature kerogen derived from both marine and terrigenous precursors. However, variations in kerogen chemistry are evident upon analysis of the pyrolysis mass spectral data in conjunction with the other geochemical analyses. Particularly diagnostic is the reduction index, Rl, a measure of H2S produced during pyrolysis. Total organic carbon, TOC, ranges from 0.6 to 6.6%, with an overall average of 2.4%. Average TOCs for these fine-grained mudstones are: late Eocene 2.5% (1 sample), Cenomanian 2.2% (6), Albian 2.0% (10), Aptian 1.3% (1), Barremian-Hauterivian 2.8% (11), late Valanginian 4.8% (3), Berriasian-early Valanginian 1.6% (7). Most of the carbonates have source-potential ratings of fair to very good of predominantly oil-prone to mixed kerogen, with only a few gas-prone samples. The ratings correlate well with the inferred depositional environments, i.e., whether oxic or anoxic. Several new organic-geochemical parameters, especially Rl, based on pyrolysis mass spectrometry of powdered whole-rock samples, support this view. Tar from fractures in laminated to bioturbated limestones of Unit IV (late Valanginian) at 535-58-4, 19-20 cm (530 m sub-bottom) appears to be mature, biodegraded, and of migrated rather than on site indigenous origin.

Clay mineralogical assemblages, Sm-Nd concentrations, Sm and Nd isotopic ratios and oxygen isotope ratios, OIS number and the age model of ODP Site 105-646

We present 40 Sm-Nd isotope measurements of the clay-size (<2 µm) fractions of sediments from the Southern Greenland rise (ODP-646) that span the last 365 kyr. These data track changes in the relative supply of fine particles carried into the deep Labrador Sea by the Western Boundary Under Current (WBUC) back to the fourth glacial-interglacial cycles. Earlier studies revealed three general sources of particles to the core site: (i) Precambrian crustal material from Canada, Greenland, and/or Scandinavia (North American Shield - NAS), (ii) Palaeozoic or younger crustal material from East Greenland, NW Europe, and/or western Scandinavia (Young Crust - YC) and (iii) volcanic material from Iceland and the Mid-Atlantic Ridge (MAR). Clay-size fractions from glacial sediments have the lowest Nd isotopic ratios. Supplies of young crustal particles were similar during glacial oxygen isotope stages (OIS) 2, 6, and 10. In contrast the mean volcanic contributions decreased relative to old craton material from OIS 10 to OIS 6 and then from OIS 6 to OIS 2. The glacial OIS 8 interval displays a mean Sm/Nd ratio similar to those of interglacials OIS 1, 5, and 9. Compared with other interglacials, OIS 7 was marked by a higher YC contribution but a similar ~30% MAR supply. The overall NAS contribution dropped by a factor of 2 during each glacial/interglacial transition, with the MAR contribution broadly replacing it during interglacials. To decipher between higher supplies and/or dilution, particle fluxes from each end member were estimated. Glacial NAS fluxes were systematically higher than interglacial fluxes. During the time interval examined, fine particle supplies to the Labrador Sea were strongly controlled by proximal ice-margin erosion and thus echoed the glacial stage intensity. In contrast, the WBUC-carried MAR supplies from the eastern basins did not change significantly throughout the last 365 kyr, except for a marked increase in surface-sediments that suggests unique modern conditions. Distal WBUC-controlled inputs from the Northern and NE North Atlantic seem to have been less variable than proximal supplies linked with glacial erosion rate.

Geochemistry of Neogene-Quaternary sediments in ODP Site 105-645

Subcontinuously cored early(?)-middle Miocene to recently deposited sediments from ODP Site 645 were studied texturally, mineralogically, and geochemically. The entire sequence contains minerals and associated chemical elements that are chiefly of detrital origin. In particular, the clay minerals, which include smectite, kaolinite, chlorite, and illite, are detrital. No obvious evidence of diagenesis with depth, of burial, of volcanism, or of hydrothermal alteration was observed. The sedimentary textures, clay mineralogy, and <2-µm fraction geochemistry of the early middle Miocene sediments (630 to 1147 mbsf) suggest the pronounced but variable influence of a southward bottom current. Two clay facies are defined. The lower one, Cj (780 to 1147 mbsf), is characterized by the great abundance of discrete smectite (with less than 15% illite interlayers), probably detrital in origin, and reworked older, discrete, smectite-rich sediments. The upper clay facies, C2 (630 to 780 mbsf), shows a net decrease of the fully expandable clay abundances, with a great abundance of mixed-layer, illite-smectite clays (60 to 80% of illite interlayers). Such clay assemblages can be inherited from paleosoils or older sedimentary rocks. An important change occurs at 630 mbsf (clay fraction) or 600 mbsf (sedimentary texture), which may be explained by the beginning of continental glaciation (630 mbsf, ~9 Ma) and the onset of ice rafting in Baffin Bay (600 mbsf, ~8 Ma). Above this level, the characteristics and modifications of the clay assemblages are controlled climatically and can be explained by the fluctuations of (1) ice-rafting, (2) speed of weak bottom currents, and (3) some supply by mud turbiditic currents. Three clay facies (C3, C4, and C5) can be defined by the abrupt increases of the inherited chlorite and illite clays.

Grain size and chemical compositions of bottom sediments from the Amur Bay

Composition of clay minerals in the <0.001 mm size fraction from the uppermost layer of bottom sediments in the northern Amur Bay was determined by X-ray powder diffraction analysis, and enrichment of 33 elements in the <0.001 mm and <0.01 mm size fractions of surface sediments from a number of sites at the marginal filter of the Razdol'naya River were studied by ICP-MS. Fe, U, and chalcophile elements occur in the highest concentrations in sediments from all sampling sites within the filter. The bottom sediments are not enriched in trace, alkali, and alkaline earth elements. Maximum concentrations of chemical elements were found in deposits from the brackish part of the marginal filter, perhaps, because of formation of Fe and Mn (Al) hydroxides. Bottom sediments at the boundary between the brackish and marine parts of the filter contain the lowest concentrations of the examined elements.