Cretaceous-Tertiary ichthyoliths of brown clay intervals

The pattern of ichthyolith distribution established in sequences with stratigraphies based on calcareous or siliceous microfossils is used to provide age correlations for three deep-sea pelagic clay intervals that lack the better known microfossils. At Site 637, approximately 25 m of brown clay in Cores 103-637A-21R through 103-637A-23R underlies upper Miocene sediments and is of Paleocene to early Eocene age. At Site 639, 1.7 m of brown clay in Core 103-639C-2R is Eocene to Oligocene. At Site 640, 3.5 m of clay in Cores 103-640A-1R and 103-640A-2R contains a Cretaceous to Paleocene sequence, with the Cretaceous/Tertiary boundary between 84 and 103 cm in Section 103-640A-2R-1.

Geochemistry of marin ash layers and epiclastic rocks from the Kerguelen Plateau

Epiclastic volcanogenic rocks recovered from the Kerguelen Plateau during Ocean Drilling Program Legs 119 and 120 comprise (pre-)Cenomanian(?) claystones (52 m thick, Site 750); a Turonian(?) basaltic pebble conglomerate (1.2 m thick, Site 748; Danian mass flows (45 m thick, Site 747); and volcanogenic debris flows of Quaternary age at Site 736 (clastic apron of Kerguelen Island). Pyroclastic rocks comprise numerous Oligocene to Quaternary marine ash layers. The epiclastic sediments with transitional mid-ocean-ridge basalt (T-MORB) origin indicate weathering (Site 750) and erosion (Site 747) of Early Cretaceous T-MORB from a then-emergent Kerguelen Plateau, connected to Late Cretaceous tectonic events. The basal pebble conglomerate of Site 748 has an oceanic-island basalt (OIB) composition and denotes erosion and reworking of seamount to oceanic-island-type volcanic sources. The vitric- to crystal-rich marine ash layers are a few centimeters thick, have rather uniform grain sizes around 60 ± 40 µm, and are a result of Plinian eruptions. Crystal-poor silicic vitric ashes may also represent co-ignimbrite ashes. The ash layers have bimodal, basaltic, and silicic compositions with a few intermediate shards. The basaltic ashes are evolved high-titanium T-MORB; a few grains in a silicic pumice lapilli layer have a low-titanium basaltic composition. The silicic ashes comprise trachytic and rhyolitic glass shards belonging to a high-K series, except for a few low-K glasses admixed to a basaltic ash layer. Feldspar and clinopyroxene compositions fit the glass chemistry: high-Ti tholeiite-basaltic glasses have Plagioclase of An40-80 and pigeonite to augite clinopyroxene compositions. Silicic ashes have K-rich anorthoclase and minor Plagioclase around An20 and ferriaugitic to hedenbergitic clinopyroxene compositions. The line of magmatic evolution for the glass shards is not compatible with simple two-end member (high-Ti T-MORB and high-K rhyolite) mixing, but favors successive Ca-Mg-Fe pyroxene, Ti magnetite, and apatite fractionation, and K-rich alkali feldspar fractionation in trachytic magmas to yield rhyolitic compositions. Plagioclase fractionation occurs throughout. This qualitative model is in basic accordance with the observed mineral assemblage. However, as the time span for explosive volcanism spans >30 m.y., this basic model cannot comply with fractional crystallization in a single magma reservoir. The ash layers resulted from highly explosive eruptions on Kerguelen and, with less probability, Heard islands since the Oligocene. The explosive history starts with widespread Oligocene basaltic ash layers that indicate sea-level or subaerial volcanism on the Northern Kerguelen Plateau. After a hiatus of 24 m.y.(?), explosive magmatic activity was vigorously renewed in the late Miocene with more silicic eruptions. A peak in explosive activity is inferred for the Pliocene-Pleistocene. The composition and evolution of Kerguelen Plateau ash layers resemble those from other hotspot-induced, oceanic-island realms such as Iceland and Jan Mayen in the North Atlantic, and the Canary Islands archipelago in the Central Atlantic.

Late Cretaceous volcaniclastic rocks at DSDP Holes 74-525A and 74-528

Volcaniclastic rocks of Late Cretaceous age occur in four out of five sites (525, 527, 528, 529) drilled on the crest and the northwest flank of the Walvis Ridge during Leg 74. They are mostly interlayered with and overlie basement in the lowermost 10-100 m of the sedimentary section. Rocks from Holes 525A and 528 were studied megascopically and microscopically, by XRD, and XRF chemical analyses of whole-rock major and trace elements were undertaken. The dominant rock of Hole 528 volcaniclastics is a fine-grained (silt to fine sand), mostly matrix-bearing (partly matrix-rich) vitric "tuff," occurring as 5-110 cm thick, partly graded layers, some of which are distinctly bedded. Volcaniclastics of Hole 525A are generally richer in sanidine crystals. Most rocks contain some nonvolcanic clasts, chiefly foraminifers and lesser amounts of shallow-water fossil debris. Scoria shards, clasts of tachylite, and fine-grained basalts as well as chemical analyses suggest a basaltic to intermediate composition for most rocks of Hole 528, whereas volcaniclastics of Hole 525A are more silicic. The occurrence of tachylite and epiclastic, coarse-grained, basaltic clasts throughout the volcaniclastic sequence at Site 528 indicates shallow-water eruptions and perhaps even ocean island volcanism. The minor occurrence in Hole 528 of trachytic? pumice shards with phenocrysts of K-feldspar and the abundance of such shards in rocks from Hole 525A indicate Plinian eruptions characteristic of more mature stages of ocean island evolution. The sedimentary structures of volcaniclastic layers and their occurrence within deep sea calcareous oozes indicate a mass flow origin. Diagenetic alteration of the volcaniclastic rocks is pronounced, and four major stages of glass shard alteration are distinguished. Despite the effects of alteration and small-scale redistribution of elements and the admixture of nonvolcanic components, there were no drastic changes in the chemical composition of the rocks, except for pronounced increases in K and Rb and decreases in Ca and Fe. The basaltic volcaniclastic rocks very much resemble basement basalts in that they are moderately evolved tholeiites derived from an LIL-enriched mantle source with Zr/Nb ratios (Hole 528) of 5 to 6. This, in conjunction with the interbedding of volcaniclastic rocks and basement lavas, indicates contemporaneous seamount or island and basement volcanic activity involving magmas derived from similar sources.

Chemical composition of Fe-Mn nodules and crusts from oceans and seas

Fluorine concentrations were determined ionometrically with an error of 0.02% in iron-manganese materials of the ocean. They were: 0.02-0.04% in ocean iron-manganese nodules, with the exception of two specimens (0.08% and 0.20% F); up to 0.02% in iron-manganese nodules of seas; 0.02-1.17% in ore crusts from ocean seamounts; and 0.02% in ore sediments of the Red Sea. Elevated fluorine content of ore crusts is associated with presence of calcium phosphate inclusions in them. Fluorine is not accumulated during iron-manganese nodule mineralization. Its average concentration in the nodules is half that in host deep-sea sediments.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Strontium and rubidium isotopes in serpentinites from ODP Site 195-1200

Subduction of the Pacific plate beneath the Mariana forearc releases fluids to the overlying mantle wedge that ascend, producing serpentinite "mud" that discharges on the ocean floor. As part of Leg 195 of the Ocean Drilling Program cores were obtained from drill-holes into the mud volcanoes. We report the isotopic composition of Sr in water squeezed from intervals of the cores, in the serpentinite mud, in leaches of the serpentinite mud, and in entrained small harzburgitic clasts. Except in the upper few meters below the seawater-mud interface, where pore water approaches seawater Sr concentration and isotopic ratio, Sr concentration and isotopic composition remain constant at 3-6 µmol/kg and ~0.7054. Because the elemental chemistry of the pore water is unlike seawater, this isotopic composition reflects fluids derived from the subducted slab, probably modified by reaction with mantle material during ascent. Higher Sr isotopic ratios, up to 0.7087, - but not with higher Sr concentrations in pore water - occur superimposed on an advection profile at 13-16 mbsf surrounding a thin layer of foraminiferal sand. Since the upward seepage velocity of slab fluids in the mud volcano vents is a few cm/yr, exchange of Sr between these carbonates and the rising fluids must have occurred within a maximum of a few hundred years, essentially instantaneously given the millions, or tens of millions, of years the mud volcanoes have been in existence. In contrast, the strontium isotopic compositions of leached serpentinite mud, and of small harzburgite clasts entrained in the mud, are always significantly greater than that of the pore water. In small harzburgite clasts the ratio reaches 0.7088, almost as high as the seawater value of 0.7092 and much higher than the value of typical mantle-derived strontium of ~0.704. The serpentinite muds and harzburgite clasts clearly equilibrated with seawater Sr when they were initially deposited at the surface of the seamount, but following burial they have not fully equilibrated with strontium in the pore water now discharging through the vents. These variations in the strontium isotopic composition of solids and pore waters are more consistent with episodic expulsion of fluids in the subduction zone than steady state flow. Whereas strontium in carbonates equilibrates isotopically within a few hundred years, strontium in buried harzburgite clasts does not equilibrate in the same time, assuming steady state rates of upward fluid flow. By inference, the harzburgite clasts and associated serpentinite mud must have been near the seafloor, unburied, for a yet undetermined but much longer period of time to have equilibrated from ~0.704 to 0.709 prior to subsequent burial. It may be possible to characterize at least the periodicity of fluid release in the mud volcano setting by investigating the zonation of strontium isotopic composition of hartzburgite clasts throughout the 60-meter deep composite cores.

Chemical composition of clinoptilolites from black clays drilled in the Northeast Atlantic

Results of a clinoptilolite study of Jurassic and Lower Cretaceous sediments from the North Atlantic recovered in DSDP holes are under discussion in the paper.

Composition of rocks, minerals, water, and gases from uplift areas of the Central Atlantic

Original geological, geophysical, lithological, mineralogical data on uplifts of the Central Atlantic are given in the book based on materials of Cruise 1 of the R/V Akademik Nikolaj Strakhov. Geological and geophysical studies include description of the obtained material and analysis of structural and morphological elements of the ocean floor. Results of lithological, petrochemical and geochemical studies were extremely innovative and develop a conceptual model. The latter include studies of petrochemical evolution of tholeiitic alkaline plate volcanism, large-scale hydrothermal transformation of basement rocks - palygorskitization, phosphatization and ferromanganese mineralization. Showing imposition Superposition of hydrogenic alteration on hydrothermally altered rocks and its role in Cenozoic history of sedimentation is shown.

Concentrations and isotopic ratios of thorium and uranium in pelagic sediments

The predictable in situ production of 230Th from the decay of uranium in seawater, and its subsequent removal by scavenging onto falling particles, provides a valuable tool for normalizing fluxes to the seafloor. We describe a new application, determination of the 232Th that dissolves in the water column and is removed to the seafloor. 232Th is supplied to the ocean in continental minerals, dissolution of which leads to a measurable standing stock in the water column. Sedimentary adsorbed 232Th/230Th ratios have the potential to provide a proxy for estimating the amount of dissolved material that enters the ocean, both today and in the past. Ten core top samples were treated with up to eight different leaching techniques in order to determine the best method for the separating adsorbed from lattice bound thorium. In addition, separate components of the sediments were analyzed to test whether clay dissolution was an important contribution to the final measurement. There was no systematic correlation between the strength of acid used in the leach and the measured 232Th/230Th ratios. In all cases clean foraminifera produced the same ratio as leaches on bulk sediment. In three out of five samples leaches performed on non-carbonate detritus in the <63 µm size fraction were also identical. Without additional water column data it is not yet clear whether there is a simple one to one correlation between the expected deep-water 232Th/230Th and that produced by leaching, especially in carbonate-rich sediments. However, higher ratios, and associated high 232Th adsorbed fluxes, were observed in areas with high expected detrital inputs. The adsorbed fraction was ~35-50% of the total 232Th in seven out of ten samples. Our 230Th normalized 232Th fluxes are reasonable by comparison to global estimates of detrital inputs to the ocean. In nine cases out of ten, the total 230Th-normalized 232Th flux is greater than predicted from the annual dust fall at each specific location, but lower than the average global detrital input from all sources.

Occurrence of hiatuses PH and NH 1 through NH 7 in DSDP holes

Miocene paleoceanographic evolution exhibits major changes resulting from the opening and closing of passages, the subsequent changes in oceanic circulation, and development of major Antarctic glaciation. The consequences and timing of these events can be observed in variations in the distribution of deep-sea hiatuses, sedimentation patterns, and biogeographic distribution of planktic organisms. The opening of the Drake Passage in the latest Oligocene to early Miocene (25-20 Ma) resulted in the establishment of the deep circumpolar current, which led to thermal isolation of Antarctica and increased global cooling. This development was associated with a major turnover in planktic organisms, resulting in the evolution of Neogene assemblages and the eventual extinction of Paleogene assemblages. The erosive patterns of two widespread hiatuses (PH, 23.0-22.5 Ma; and NH 1, 20-18 Ma) indicate that a deep circumequatorial circulation existed at this time, characterized by a broad band of carbonate-ooze deposition. Siliceous sedimentation was restricted to the North Atlantic and a narrow band around Antarctica. A major reorganization in deep-sea sedimentation and hiatus distribution patterns occurred near the early/middle Miocene boundary, apparently resulting from changes in oceanic circulation. Beginning at this time, deep-sea erosion occurred throughout the Caribbean (hiatus NH 2, 16-15 Ma), suggesting disruption of the deep circumequatorial circulation and northward deflection of deep currents, and/or intensification of the Gulf Stream. Sediment distribution patterns changed dramatically with the sudden appearance of siliceous-ooze deposition in the marginal and east equatorial North Pacific by 16.0 to 15.5 Ma, coincident with the decline of siliceous sedimentation in the North Atlantic. This silica switch may have been caused by the introduction of Norwegian Overflow Water into the North Atlantic acting as a barrier to outcropping of silica-rich Antarctic Bottom Water. The main aspects of the present oceanic circulation system and sediment distribution pattern were established by 13.5 to 12.5 Ma (hiatus NH 3), coincident with the establishment of a major East Antarctic ice cap. Antarctic glaciation resulted in a broadening belt of siliceous-ooze deposition around Antarctica, increased siliceous sedimentation in the marginal and east equatorial North Pacific and Indian Oceans, and further northward restriction of siliceous sediments in the North Atlantic. Periodic cool climatic events were accompanied by lower eustatic sea levels and widespread deep-sea erosion at 12 to 11 Ma (NH 4), 10 to 9 Ma (NH 5), 7.5 to 6.2 Ma (NH 6), and 5.2 to 4.7 Ma (NH 7).

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.