Geochemistry of mafic clasts of ODP Holes 125-778A and 125-779A

Clasts of metamorphosed mafic igneous rock of diverse composition were recovered in two drill sites on a serpentine mud volcano in the outer Mariana forearc during Ocean Drilling Program Leg 125. These clasts are xenolithic fragments that have been entrained in the rising serpentine mud, and make up less that 9% of the total rock recovered at Sites 778 and 779. Most samples are metabasalt or metadiabase, although one clast of possible boninite and one cumulate gabbro were recovered. On the basis of trace element signatures, samples are interpreted to represent both arc-derived and mid-ocean ridge-derived compositions. Rocks with extremely low TiO2 (<0.3 wt%) and Zr (<30 ppm) are similar to boninite series rocks. Samples with low TiO2 (<0.9 wt%) and Zr (<50 ppm) and extreme potassium enrichment (K2O/Na2O >3.9) may represent island arc rocks similar to shoshonites. However, the K2O/Na2O ratios are much higher than those reported for shoshonites from modem or ancient arcs and may be the result of metamorphism. Samples with moderate TiO2 (1.4 to 1.5 wt%) and Zr (72 to 85 ppm) are similar to rocks from mid-ocean ridges. A few samples have TiO2 and Zr intermediate between island arc and mid-ocean ridge basalt-like rocks. Two samples have high iron (Fe2O3* = >12.8 to 18.5 wt%) (Fe2O3* = total iron calculated as Fe2O3) and TiO2 (>2.3 wt%) and resemble FeTi basalt recovered from mid-ocean ridges. Metamorphism in most samples ranges from low-temperature zeolite, typical of ocean floor weathering, to prehnite-pumpellyite facies and perhaps lower greenschist. Blue amphibole and lawsonite minerals are present in several samples. One diabase clast (Sample 9) exhibits Ca enrichment, similar to rodingite metamorphism, typical of mafic blocks in serpentinized masses. The presence of both low-grade (clays and zeolites) and higher grade (lawsonite) metamorphism indicates retrograde processes in these clasts. These clasts are fragments of the forearc crust and possibly of the subducting plate that have been entrained in the rising serpentine and may represent the deepest mafic rocks ever recovered from the Mariana forearc. The variable compositions and degree of metamorphism of these clasts requires at least two tectonic origins. The recovery of clasts with mid-ocean ridge and arc chemical affinities in a single drill hole requires these clasts to have been "mixed" on a small scale either (1) in the forearc crustal sequence, or (2) after inclusion in the rising serpentine mud. The source of the MORB-like samples and an explanation for the presence of both MORB-like and arc-like rocks in close proximity is critical to any model of the evolution of the Mariana forearc. The source of the MORB-like samples likely will be one (or more) of the following: (1) accretion of Pacific plate lithosphere, (2) remnants of original forearc crust (trapped plate), (3) volcanism in the supra-subduction zone (arc or forearc) environment, or (4) derivation from the subducting slab by faulting along the dÈcollement.

Geochemistry of the oceanic crust from ocean drilling samples

This book presents new data on chemical and mineral compositions and on density of altered and fresh igneous rocks from key DSDP and ODP holes drilled on the following main tectonomagmatic structures of the ocean floor: 1. Mid-ocean ridges and abyssal plains and basins (DSDP Legs 37, 61, 63, 64, 65, 69, 70, 83, and 91 and ODP Legs 106, 111, 123, 129, 137, 139, 140, 148, and 169); 2. Seamounts and guyots (DSDP Legs 19, 55, and 62 and ODP Legs 143 and 144); 3. Intraplate rises (DSDP Legs 26, 33, 51, 52, 53, 72, and 74 and ODP Legs 104, 115, 120, 121, and 183); and 4. Marginal seas (DSDP Legs 19, 59, and 60 and ODP Legs 124, 125, 126, 127, 128, and 135). Study results of altered gabbro from the Southwest Indian Ridge (ODP Leg 118) and serpentinized ultramafic rocks from the Galicia margin (ODP Leg 103) are also presented. Samples were collected by the authors from the DSDP/ODP repositories, as well as during some Glomar Challenger and JOIDES Resolution legs. The book also includes descriptions of thin sections, geochemical diagrams, data on secondary mineral assemblages, and recalculated results of chemical analyses with corrections for rock density. Atomic content of each element can be quantified in grams per standard volume (g/1000 cm**3). The suite of results can be used to estimate mass balance, but parts of the data need additional work, which depends on locating fresh analogs of altered rocks studied here. Results of quantitative estimation of element mobility in recovered sections of the upper oceanic crust as a whole are shown for certain cases: Hole 504B (Costa Rica Rift) and Holes 856H, 857C, and 857D (Middle Valley, Juan de Fuca Ridge).

(Table 1) Mineralogy of veins in basalts at DSDP Hole 61-462A

Numerous veins are present in basalts recovered from Hole 462A, Leg 61 of the Deep Sea Drilling Project. Three mineral assemblages are recognized and stratigraphically controlled. These assemblages are (1) a zeolite-bearing, quartz-poor assemblage which occurs from Core 44 to the bottom of the hole and contains smectite, clinoptilolite, calcite, pyrite, ± chabazite, ± analcime, ± quartz, ± apophyllite, ± talc (?); (2) a quartz-rich, pyrite-bearing assemblage, found between Cores 19 and 29, which contains smectite, calcite, quartz, and pyrite; and (3) a quartz-rich, celadonite-bearing assemblage which occurs from Cores 14 through 17 and contains smectite, calcite, quartz, celadonite, and Fe oxide. These data are interpreted to represent two episodes of vein mineral formation with an oxidative overprint on the more recent. The first episode followed the outpourings of basaltic lavas onto the sea floor. Zeolite-bearing veins were formed at elevated temperatures under low PCO2 while the thermal gradient was high and before a cover of calcareous sediments had formed. The second mineralization episode followed injection of basalt and microdiabase sills into a thick layer of sediments, and produced all the vein minerals now occurring between Cores 14 and 29. These veins formed at lower temperature and higher PCO2 than zeolite-bearing veins. The presence of pyrite indicates a nonoxidative environment. After the initial formation of these veins, oxygenated seawater diffused through the sedimentary cover and oxidized the pyrite and smectite, forming celadonite and Fe oxides.

Mineralogy of sediments from the Exmouth Plateau and Argo Basin

Correlation of mineral associations from sediment recovered on the northwestern Australian continental margin document the juvenile-to-mature evolution of a segment of the Indian Ocean. Lower Cretaceous sediments contain sandy-to-silty radiolarian claystone that consists of highly smectitic mixed-layered illite/smectite (I/S) in addition to minor amounts of diagenetic pyrite, barite, and rhodochrosite. These immature, poorly sorted sediments were derived from nearby continental margin sources. Discrete bentonite layers and abundant smectite are the alteration products of volcanic material deposited during early basin formation. Abundant quartz-replaced radiolarian tests suggest high surface-water productivity, and calcareous fossils indicate water depths were above the calcite compensation depth (CCD) in the juvenile Indian Ocean. The increase in pelagic carbonate from the mid- to Late Cretaceous signals the transition to mature, open-ocean conditions. Similar to other slowly deposited contemporaneous deep-sea sediments, mid- to Upper Cretaceous sediments of the northwestern margin of Australia contain palygorskite. This palygorskite is associated with calcareous sediment across the ooze-to-chalk transition, detrital mixed-layered I/S, and zeolite minerals in places. This palygorskite occurs above the transformation from opal-A to opal-CT. The underlying opal-CT sediment contains abundant smectite and zeolite minerals. Calcareous sediment dominates the Cenozoic, except at abyssal sites that were not inundated by calcareous turbidites. Paleocene and Eocene sediments contain abundant smectite and zeolite minerals derived from the alteration of volcanic material. Palygorskite was found to be associated with sepiolite and dolomite in Miocene sediments from Site 765 in the Argo Basin. Pliocene and Quaternary sediments contain detrital kaolinite and mixed-layered I/S, abundant opal-A radiolarian tests, and minor amounts of pyrite

Major and trace element analyses from DSDP Hole 26-253 at the Ninetyeast Ridge in the Indian Ocean

A basaltic sequence of Eocene submarine-erupted pyroclastic sediments totals at least 388 m at DSDP Site 253 on the Ninetyeast Ridge. These fossiliferous hyaloclastic sediments have been erupted and fragmented by explosive volcanism (hydroexplosions) in shallow water. The occurrence of interbedded basaltic ash-fall tuffs within the younger horizons of the hyaloclastic sequence marks the emergence of some Ninetyeast Ridge volcanic vents above sea level. Considerable textural variation allows subdivision of the sequence into six informal lithostratigraphic units. Hydrothermal and diagenetic alteration has caused the complete replacement of all original glass by smectites, and the introduction of abundant zeolite and calcite cements. The major and trace element contents of the hyaloclastites vary due to the alteration, and the admixture of biogenous calcite. On a calcium carbonate-free basis systematic variations are recognisable. Mg, Ni, Cr and Cu are enriched, and Li and Zn depleted in the three older units relative to the younger three. The chemical variability is reflected by the development of saponite in the older part of the sequence and montmorillonite in the younger; and by the presence of a quartz-normative basalt flow occurring in Unit II, in contrast to the Mg-rich highly olivine-normative basalt at the base of the sequence. The younger and older parts of the sequence therefore appear to have been derived from magmas of different chemistry. The sequence, like other basaltic rocks recovered from the Ninetyeast Ridge, is enriched in the light relative to the heavy rare earth elements (REE) although the REE contents vary unsystematically with depth, probably because of the high-temperature subaqueous alteration and the presence of biogenous calcite. This REE data indicates that the Ninetyeast Ridge volcanism was different from that which produces mid-ocean ridge basalts.

Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.

(Table 1) Stabile isotopes at DSDP Leg 55 Holes

Deep sea drilling on four seamounts in the Emperor Seamount chain revealed that Paleogene shallow-water carbonate sediments of the "bryozoan-algal" facies crown the basalt edifices. According to the biofacies model of Schlanger and Konishi (1966, 1975), this bryozoan- algal assemblage suggests that the seamounts formed in cooler, more northerly waters than those presently occupied by the island of Hawaii; i.e., the paleolatitudes of formation were greater than 20 °N. Moving southward toward the youngest member of the seamount chain, a facies gradient indicative of warmer waters was observed. This gradient is interpreted as a reflection of a northward shift in isotherms during the time span in which the seamounts were progressively formed (Savin et al., 1975). On all seamounts, sedimentation at the drilling sites occurred in a high-energy environment with water depths of approximately 20 meters. Early-stage carbonate diagenesis began in the phreatic zone in the presence of meteoric water, but proceeded after subsidence of the seamounts into intermediate sea waters, where the bulk, stable isotopic composition was determined. The subsidence into intermediate waters was rapid, and permitted establishment of an isotopic equilibrium which, like the facies gradient, reflects the northward shift in isotherms during the Paleogene. Calcite and zeolite cements comprise the later-stage diagenesis, and originated from solutions arising from the hydrolysis of the underlying basalt. In conclusion, the results of this study of the shallow-water carbonate sediments are not inconsistent with a paleolatitude of formation for Suiko Seamount (Site 433) of 26.9 ±3.5 °N, as determined by paleomagnetic measurements (Kono, 1980).

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Petrology and geochemistry of oceanic intraplate sheet-flow basalts at DSDP Hole 89-462A

Reentry of Hole 462A during Leg 89 resulted in the penetration of a further 140 m of basalt sheet-flows similar to those found during Leg 61 at the same site. Twelve volcanic units (45 to 56) were recognized, comprising a series of rapidly extruded, interlayered aphyric and poorly clinopyroxene-plagioclase-olivine phyric, nonvesicular basalts. All exhibit variable, mild hydration and oxidation, relative to fresh oceanic basalts, produced under reducing, low-CO2-activity conditions within the zeolite facies. Secondary assemblages are dominated by smectites, zeolites, and pyrite, produced by low-temperature reaction with poorly oxygenated seawater. No systematic mineralogical or chemical changes are observed with depth, although thin quenched units and more massive hypocrystalline units exhibit slightly different alteration parageneses. Chemically, the basalts are olivine- and quartz-normative tholeiites, characterized by low incompatible-element abundances, similar to mildly enriched MORB (approaching T-type), with moderate, chrondite-normalized, large-ionlithophile- element depletion patterns and generally lower or near-chrondritic ratios for many low-distribution-coefficient (KD) element pairs. In general, relative to cyclic MORB chemical variation, they are uniform throughout, although 3 chemical megagroups and 22 subgroups are recognized. It is considered that the megagroups represent separate low-pressure-fractionated systems (olivine + Plagioclase ± clinopyroxene), whereas minor variations within them (subgroups) indicate magma mixing and generation of near-steady-state conditions. Overall, relatively minor fractionation coupled with magma mixing produced a series of compositionally uniform lavas. Parental melts were produced by similar degrees of partial melting, although the source may have varied slightly in LIL-element content.

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.

Petrographic description and geochemistry of basalts and altered volcanic rocks from ODP Leg 183 sites

The basalts recovered during Legs 183 and 120 from the southern, central, and northernmost parts of the Kerguelen Plateau (Holes 1136A, 1138A, 1140A, and 747C, respectively), as well as those recovered from the eastern part of the crest of Elan Bank (Hole 1137A), represent derivates from tholeiitic melts. In the northern part of the Kerguelen Plateau (Hole 1140A), basalts may have formed from two sources located at different depths. This is reflected in the presence of both low- and high-titanium basalts. The basalts are variably altered by low-temperature hydrothermal processes (at temperatures up to 120°C), and some are affected by subaerial weathering. The hydrothermal alteration led mainly to the formation of smectites, chlorite minerals, mixed-layer hydromica-smectite and smectite-chlorite minerals, hydromica, serpentine(?), clinoptilolite, heulandite, stilbite, analcime, mordenite, thomsonite, natrolite(?), calcite, quartz, and dickite(?). Alteration of extrusive basalts is mainly related to horizontal fluid flow within permeable contact zones between lava flows. Under a nonoxidizing environment of alteration, the tendency to lose most of elements, including rare earth elements, from basalts dominates. Under on oxidizing environment, basalts accumulate many elements.

Sedimentological and geochemical characteristics of upper Cretaceous and lower Tertiary sediments of ODP Hole 108-661A

Based on sedimentological and geochemical data, the Upper Cretaceous and Tertiary sequence at Ocean Drilling Program Site 661 was subdivided into four intervals: Interval I (Campanian age) is characterized by sediments deposited below the calcite compensation depth (CCD) inside a high-productivity area and well-oxygenated bottom waters, indicated by the absence of carbonate, the major occurrence of zeolites and opal-CT, and intense bioturbation. Very fine-grained siliciclastic sediments and the lack of any erosional features suggest a low-energy environment. The terrigenous fraction was probably supplied by winds from the nontropical areas in South Africa. Interval II (Maestrichtian age) is characterized by high-amplitude variations in the carbonate content indicative of a deposition above the CCD, superimposed by (climate-controlled) short-term fluctuations of the CCD. The absence of both zeolites and opal-CT imply a position of Site 661 outside high-productivity areas. The first occurrence of higher amounts of kaolinite (especially during the middle Maestrichtian) suggests the onset of a terrigenous sediment supply from tropical areas. Interval III (between uppermost Cretaceous to early Tertiary) is characterized by the absence of carbonate and zeolites, interpreted as deposition below the CCD and outside an oceanic high-productivity belt. The kaolinite-over-illite dominance suggests a terrigenous sediment supply from tropical areas. Interval IV (between early Tertiary and Miocene age) is characterized by the occurrence of black manganeserich layers, major nodules/pebbles, and erosional surfaces, indicating phases of extremely reduced sediment accumulation and bottom-current activities. In the lower part of this interval (?Eocene age), higher amounts of zeolites occur, which suggest a higher oceanic productivity caused by equatorial upwelling. The source area of the terrigenous sediment fraction at Site 661 was the tropical region of northwest Africa, as suggested by the kaolinite-over-illite dominance.