Mineralogy, geochemistry and selected chemical formulas of sediments from ODP Holes 161-986B and 161-977A

Upper Miocene to Pleistocene hemipelagites and resedimented facies recovered at Holes 976B and 977A (Leg 161) in the Alboran Basin consist mainly of biogenic and detrital components, with a minor contribution of neoformed mineral phases. Diagenetic processes have not obliterated the primary deposition signal, and therefore detrital components (quartz, feldspar, detrital dolomite, rock fragments, and clays) provide information about source rocks and provenances. No major bulk or clay mineralogy differences were recognized between resedimented and hemipelagic facies; in fact, similar mineral assemblages in both types of facies suggest common source rocks. However, mineral abundance fluctuations can be related to climate variations and tectonic factors, as the main controls of sediment fill of this basin. A marked increase in smectites in Messinian sediments suggests an extensive development of soils during that time, probably favored by the alternation of wet and dry climate episodes and the relative aridification of the Mediterranean borderlands. A notable increase in detrital components suggests a sea-level fall and/or tectonic uplift during the late Pliocene. The significant increase in detrital dolomite in the uppermost Pliocene deposits suggests the uplift of dolomite-rich rocks as source areas. Mineral components in Pleistocene sediments indicate increasing tectonic stability, and clay-mineral fluctuations during the Pleistocene can be related not only to tectonic events, but also to alternating cooling and warming periods.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

(Table 1) Chemical composition of volcanic rocks from the Mariisky sequence and extrusive vent rocks of the Mary Cape, Schmidt Peninsula (North Sakhalin)

Early Cretaceous volcanic rocks of the Mariisky sequence and Early Cenozoic extrusive-vent rocks of the Mary Cape are exposed at the most northwest of the Schmidt Peninsula, North Sakhalin. In chemical composition, all the rocks are subdivided into four groups. Three groups include volcanic rocks of the Mariisky sequence, which consists, from bottom to top, of calc-alkaline rocks, transitional calc-alkaline-tholeiite rocks, and incompatible element-depleted tholeiites. These rocks show subduction geochemical signatures and are considered as a fragment of the Moneron-Samarga island arc system. Trace-element modeling indicates their derivation through successive melting of a garnet-bearing mantle and garnet-free shallower mantle sources containing amphibole; pyroxene; and, possibly, spinel. The mixed subduction and intra-plate characteristics of the extrusive vent rocks of the Mary Cape attest to their formation in a transform continental margin setting.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Geochemistry of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

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.

Geochemistry of Ninetyeast Ridge basaltic glasses

The Ninetyeast Ridge (NER), a north-south striking, 5,000 km long, 77 to 43 Ma chain of basaltic submarine volcanoes in the eastern Indian Ocean formed as a hotspot track created by rapid northward migration of the Indian Plate over the Kerguelen hotspot. Based on the major and trace element contents of unaltered basaltic glasses from six locations along the NER, we show that the NER was constructed by basaltic magma derived from at least three geochemically distinct mantle sources: (1) a source enriched in highly incompatible elements relative to primitive mantle like the source of the 29-24 Ma flood basalts in the Kerguelen Archipelago; (2) an incompatible element-depleted source similar to the source of Mid-Ocean Ridge Basalt (MORB) erupted along the currently active Southeast Indian Ridge (SEIR); and (3) an incompatible element-depleted source that is compositionally and mineralogically distinct from the source of SEIR MORB. Specifically, this depleted mantle source was garnet-bearing and had higher Y/Dy and Nb/Zr, but lower Zr/Sm, than the SEIR MORB source. We infer that this third source formed as a garnet-bearing residue created during a previous melting event, perhaps an initial partial melting of the mantle hotspot. Subsequently, this residue partially melted over a large pressure range, from slightly over 3 GPa to less than 1 GPa, and to a high extent (~ 30%) thereby creating relatively high SiO2 and FeO contents in some NER basalts relative to SEIR MORB.

Platinum-group element abundances in background samples and the K-T boundary interval from DSDP Hole 91-596 (Table 2)

New data on Ru/Ir abundance ratios are presented for nonmarine (Hell Creek, Montana; Frenchman River, Saskatchewan) and marine Cretaceous-Tertiary boundary sites (Brazos River, Texas; Beloc, Haiti; DSDP 577 and DSDP 596). The Ru/Ir ratio varies from 0.5 to 1 within 4000 km of Chicxulub and increases to 2-3 at paleodistances (65 Ma) of up to 12,000 km from the impact site. For CI chondrites, Ru/Ir = 1.5. A ballistic model of ejecta cloud cooling and expansion, which employs the available vapor-pressure versus temperature data for Ru and It, predicts qualitatively similar global variation in the Ru/Ir ratio but by only a factor of 1.5. We infer that several other factors, such as remobilization of PGE during diagenesis, preferential oxidation of Ru, condensation kinetics and atmospheric chemical and circulation processes, may account for the observed larger Ru/Ir variation.