Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

Distribution of biological, anthropogenic, and volcanic constituents in the San Francisco Bay Coastal System

Although conventional sediment parameters (mean grain size, sorting, and skewness) and provenance have typically been used to infer sediment transport pathways, most freshwater, brackish, and marine environments are also characterized by abundant sediment constituents of biological, and possibly anthropogenic and volcanic, origin that can provide additional insight into local sedimentary processes. The biota will be spatially distributed according to its response to environmental parameters such as water temperature, salinity, dissolved oxygen, organic carbon content, grain size, and intensity of currents and tidal flow, whereas the presence of anthropogenic and volcanic constituents will reflect proximity to source areas and whether they are fluvially- or aerially-transported. Because each of these constituents have a unique environmental signature, they are a more precise proxy for that source area than the conventional sedimentary process indicators. This San Francisco Bay Coastal System study demonstrates that by applying a multi-proxy approach, the primary sites of sediment transport can be identified. Many of these sites are far from where the constituents originated, showing that sediment transport is widespread in the region. Although not often used, identifying and interpreting the distribution of naturally-occurring and allochthonous biologic, anthropogenic, and volcanic sediment constituents is a powerful tool to aid in the investigation of sediment transport pathways in other coastal systems.

Contents of major components, U, and Th in bones and bone debris

Uranium and thorium contents, as well as their distribution patterns have been studied in biogenic phosphates from the Atlantic and Pacific Oceans. Differently lithified fish remains (bones, scales, teeth) and marine mammal bones (ribs, vertebras, earbones) collected from both reduced shelf sediments and oxidized pelagic ones have been analyzed. U content in the material varies from 0.7 to 700 ppm, and Th content - from <0.5 to 14 ppm. U/Th ratio varies from 0.16 to 400. Contents of both elements increase with lithification of biogenic phosphates. U concentration is more intense on shelves, whereas thorium concentration increases in pelagic areas. Partial positive correlation of U and Th with Fe and negative correlation of U with organic carbon are noted. The latter corresponds to higher lithification of biogenic phosphates. Calcium phosphate transformed from hydroxyapatite to fluorcarbonate-apatite is the main carrier of U, while transformed organic matter is a minor agent. Thorium is mainly bound with Fe.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

Petrology of ODP Leg 210 and Leg 173, and DSDP Leg 47 sites

Sand detrital modes of Albian-Eocene clastic gravity-flow deposits cored and recovered at Ocean Drilling Program Site 1276 reflect the postrift geologic evolution of the Newfoundland passive continental margin. Cretaceous sandstone compositions (average: Q57F23L20; Ls%Lsc = 35; total%bioclasts = 3) are consistent with a source on Grand Banks such as Avalon Uplift. Their relatively low potassium feldspar (Qm71K8P21) contents distinguish them from Iberian sandstones and appear to preclude an easterly source during the early history of the ocean basin. Isolated volcaniclastic input near the Paleocene/Eocene boundary (~60 Ma) at Site 1276 is also present in Iberian samples of this age, suggesting that magmatism was widespread across the North Atlantic during this time frame; the source(s) of this volcanic debris remains equivocal. In the Eocene, the development of carbonate bank facies on the shelf marks a profound compositional change to calcareous grainstones (average: Q27F11L62; Ls%Lsc = 82; total%bioclasts = 55) in basinal gravity-flow deposits at Site 1276. This calcareous petrofacies is present on the Iberian margin and in the Pyrenees, suggesting that it was a regional event. The production and downslope redistribution of carbonate debris, including bioclastic and lithic fragments, was likely eustatically controlled. The Newfoundland (Site 1276 and Jeanne d'Arc Basin) sandstones are mainly quartzolithic. Their composition and the contrast in composition between them and more quartzofeldspathic sandstones from the Iberian margin are likely a product of rifting along a Paleozoic suture zone separating distinct basement terranes. This prerift geologic setting contrasts with that of rifts developed within other cratonic settings with variable amounts of synrift volcanism. When synthesized, the spectrum of synrift and postrift sand compositions produces a general model of passive margin (rift-to-drift) sandstone provenance.

Chemical composition of soils and rocks from King George Island

Both the olivine-hearing tholeiite basalts of the island and the brown soils which have developed on the basalts contain 2-20% of a swelling clay mineral. It emerges from chemical, optical, X-ray diffraction and differential thermal analytical studies that this clay mineral is a Mg-rich, Fe2+ and AI-bearing tri-octahedral smectite, e. g. Mg-saponite. Due to petrographic and crystal chemical properties the saponite should have been formed by hydrothermal alteration of the primary Mg-Fe-minerals olivine and clinopyroxene. The soils consist of plagioclase, saponite and goethite which has been formed by chemical weathering within the soils. In the uppermost layer some of the soils contain humic substances and phosphatic material, the latter may be related to the recent production of guano.

Chemical, isotopic and mineral compositions of basal metalliferous sediments from DSDP Legs 5 and 7

Sediments from near the basement of a number of Deep Sea Drilling Project (DSDP) sites, from the Bauer Deep, and from the East Pacific Rise have unusually high transition metal-to-aluminum ratios. Similarities in the chemical, isotopic, and mineralogical compositions of these deposits point to a common origin. All the sediments studied have rare-earth-element (REE) patterns strongly resembling the pattern of sea water, implying either that the REE's were coprecipitated with ferromanganese hydroxyoxides (hydroxyoxides denote a mixture of unspecified hydrated oxides and hydroxides), or that they are incorporated in small concentrations of phosphatic fish debris found in all samples. Oxygen isotopic data indicate that the metalliferous sediments are in isotopic equilibrium with sea water and are composed of varying mixtures of two end-member phases with different oxygen isotopic compositions: an iron-manganese hydroxyoxide and an iron-rich montmorillonite. A low-temperature origin for the sediments is supported by mineralogical analyses by x-ray diffraction which show that goethite, iron-rich montmorillonite, and various manganese hydroxyoxides are the dominant phases present. Sr87/Sr86 ratios for the DSDP sediments are indistinguishable from the Sr87/Sr86 ratio in modern sea water. Since these sediments were formed 30 to 90 m.y. ago, when sea water had a lower Sr87/Sr86 value, the strontium in the poorly crystalline hydroxyoxides must be exchanging with interstitial water in open contact with sea water. In contrast, uranium isotopic data indicate that the metalliferous sediments have formed a closed system for this element. The sulfur isotopic compositions suggest that sea-water sulfur dominates these sediments with little or no contribution of magmatic or bacteriologically reduced sulfur. In contrast, ratios of lead isotopes in the metalliferous deposits resemble values for oceanic tholeiite basalt, but are quite different from ratios found in authigenic marine manganese nodules. Thus, lead in the metalliferous sediments appears to be of magmatic origin. The combined mineralogical, isotopic, and chemical data for these sediments suggest that they formed from hydrothermal solutions generated by the interaction of sea water with newly formed basalt crust at mid-ocean ridges. The crystallization of solid phases took place at low temperatures and was strongly influenced by sea water, which was the source for some of the elements found in the sediments.

Planktic foraminiferal assemblages in sediments of four ODP Leg 198 holes

A pulse of intense carbonate dissolution occurred during the early late Paleocene at 58.4 Ma. A prominent 5 to 25 cm-thick dark brown clay-rich calcareous nannofossil ooze was found on Shatsky Rise at Sites 1209, 1210, 1211, and 1212 during Ocean Drilling Program Leg 198. The layer corresponds to the lower part of planktonic foraminiferal Zone P4 and coincides with the evolutionary first occurrence of the nannolith Heliolithus kleinpellii, an important component of late Paleocene assemblages and a marker for the base of Zone CP5. The clay-rich layer contains common crystals of phillipsite, fish teeth, and phosphatic micronodules and corresponds to a prominent peak in magnetic susceptibility that probably reflects these high amounts of detrital and authigenic materials. Detailed quantitative analysis of planktonic foraminiferal assemblages across the clay-rich nannofossil ooze layer shows that fundamental changes in faunal composition occurred before, during, and after deposition of the clay-rich ooze. Planktonic foraminifers in the clay-rich layer are characterized by a low-diversity, largely dissolved assemblage dominated by representatives of the genus Igorina (mainly Igorina tadjikistanensis and Igorina pusilla). Conversely, Igorina albeari, morozovellids, acarininids, globanomalinids, subbotinids, and chiloguembelinids are common below the clay-rich layer, almost disappear within it, and reappear in low abundances above the clay-rich layer. These changes in faunal compositions are likely a response to a change in carbonate saturation that caused increased dissolution on the seafloor owing to the shoaling of the lysocline and the carbonate compensation depth.

(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Observations and rare earth element composition of manganese nodules during Atlantis cruise AT266, Blake Plateau

An area of about 22,000 km² on the northern Blake Plateau, off the coast of South Carolina, contains an estimated 2 billion metric tons of phosphorite concretions, and about 1.2 billion metric tons of mixed ferromanganese-phosphorite pavement. Other offshore phosphorites occur between the Blake Plateau and known continental deposits, buried under variable thicknesses of sediments. The phosphorite resembles other marine phosphorites in composition, consisting primarily of carbonate-fluorapatite, some calcite, minor quartz and other minerals. The apatite is optically pseudo-isotropic and contains about 6% [CO3]**2- replacing [PO4]**3- in its structure. JOIDES drillings and other evidence show that the phosphorite is a lag deposit derived from Miocene strata correlatable with phosphatic Middle Tertiary sediments on the continent. It has undergone variable cycles of erosion, reworking, partial dissolution and reprecipitation. Its present form varies from phosphatized carbonate debris, loose pellets, and pebbles, to continuous pavements, plates, and conglomeratic boulders weighing hundreds of kilograms. No primary phosphatization is currently taking place on the Blake Plateau. The primary phosphate-depositing environment involved reducing conditions and required at least temporary absence of the powerful Gulf Stream current that now sweeps the bottom of the Blake Plateau and has eroded away the bulk of the Hawthorne-equivalent sediments with which the phosphorites were once associated.

Annotated record of the detailed examination of Mn deposits from the R/V Rig Seismic Cruise 11 (BMR 66) in 1986 over the Great Australian Bight Basin area

Late Cretaceous and younger sediments dredged from the upper continental slope and canyon walls in the Great Australian Bight Basin between 126° and 136°E broadly confirm the stratigraphy which had been established previously from scattered exploration wells. Late Cretaceous to Early Eocene marine and marginal marine terrigenous sediments are overlain by Middle Eocene and younger pelagic carbonate (fine limestone and calcareous ooze). The samples provide the first evidence of truly marine Maastrichtian sedimentation, with abundant calcareous nannoplankton, on the southern margin of the continent. Other samples of interest include Precambrian sheared granodiorite on the upper slope south of Eyre Terrace, Paleocene phosphatic sediment in 'Eucla' Canyon at 128° 30'E, and terrigenous Early Miocene mudstone at 133° 20' and 134° 50'E. The mudstone is of note as an exception to the uniform pelagic carbonate wackestone and ooze which characterise Middle Eocene and younger sedimentation at all other sites. Fragments of alkali basalt lava of unknown age were recovered in 'Eucla' Canyon. Cores are mostly pelagic calcareous ooze, but those from submarine canyons include terrigenous turbidites.

(Table 2) Grain composition of sediments from ODP Hole 161-974B and from beach samples

Miocene to Pleistocene sand and sandstone were recovered at Ocean Drilling Program Site 974 in the Tyrrhenian Basin and Sites 976 and 977 in the Alboran Basin. Sand detrital modes were determined for 45 samples from these sites, as well as 10 samples of Spanish beach sand. At Site 974, the Pleistocene section includes a number of volcaniclastic (vitric ash) and terrigenous sand layers; the latter are heterogeneous and contain sedimentary and metamorphic lithic fragments. Submarine canyon and onshore drainage patterns suggest that the most likely source of this sediment is the Tiber River drainage basin in central Italy, where a Pleistocene volcanic field is superimposed on Apennine orogenic rocks. In contrast, the Miocene sand in Unit III at Site 974 may have been derived from local basement highs. The quartzolithic composition and preponderance of metamorphic and sedimentary lithic debris in sand samples from Unit II at Site 976, Unit I at Sites 977 and 978, and Unit I at Site 979 are consistent with derivation from metamorphic rocks and sedimentary cover sequences that crop out in the Betic Cordillera of southern Spain (976-978) and in the Rif of Northern Africa (979). The sedimentary to metamorphic lithic fragment ratios in these samples reflect the relative proportion of metamorphic and sedimentary rocks exposed in onshore source terranes. In contrast, the source of the few quartzose Pleistocene sands at Site 976 was likely the Flysch Trough Units that crop out near Gibraltar. The significant volcanic component in certain intervals at Sites 976 (upper Miocene) and 977 (lower Pliocene to Miocene) is consistent with widespread volcanic activity during basin inception and development. Mean sand detrital modes for sand subgroups from both the Alboran and Tyrrhenian Basin sites plot in the Recycled Orogenic and Magmatic Arc compositional fields of Dickinson et al. (1983, doi:10.1130/0016-7606(1983)94<222:PONAPS>2.0.CO;2), reflecting the hybrid tectonic histories of these basins.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.