Paleomagnetic of igneous rocks of ODP Leg 114

A paleomagnetic study was made of 12 samples of trachytic basalt from the base of ODP Hole 698A on the Northeast Georgia Rise (southwest Atlantic) and four samples of andesitic basalt and nine samples of volcanic breccia from the base of ODP Hole 703A on the Meteor Rise (southeast Atlantic). The magnetic intensities of the Hole 703A samples are anomalously low, possibly reflecting alteration effects. The mean magnetic intensity of the Hole 698A samples is high, and compatible with the model of Bleil and Petersen (1983) for the variation of magnetic intensity with age in oceanic basalts, involving progressive low-temperature oxidation of titanomagnetite to titanomaghemite for some 20 m.y. followed by inversion to intergrowths of magnetite and other Fe-Ti oxides during the subsequent 100 m.y. These results support the interpretation of the Hole 698A basalts as true oceanic basement of Late Cretaceous age rather than a younger intrusion. Well-defined stable components of magnetization were identified from AF and thermal demagnetization of the Hole 698A basalts, and less well-defined components were identified for the Hole 703A samples. Studies of the magnetic homogeneity of the Hole 698A basalts, involving harmonic analysis of the spinner magnetometer output, indicate the presence of an unevenly distributed low-coercivity component superimposed on the more homogeneous high-coercivity characteristic magnetization. The former component is believed to reside in irregularly distributed multidomain magnetite grains formed along cracks within the basalt, whilst the latter resides in more uniformly distributed finer magnetic grains. The inclination values for the high-coercivity magnetization of five Hole 698A basalt samples form an internally consistent set with a mean value of 59° ± 5°. The corresponding Late Cretaceous paleolatitude of 40° ± 5° is shallower than expected for this site but is broadly compatible with models for the opening of the South Atlantic involving pivoting of South America away from Africa since the Early Cretaceous. The polarity of the stable characteristic magnetization of the Site 698 basalts is normal. This is consistent with their emplacement during the long Campanian to Maestrichtian normal polarity Chron C33N.

Paleomagnetic properties of igneous rocks from several DSDP and ODP sites, western Pacific

Oceanic basalts and other related igneous rocks are considered excellent recorders of the Earth's paleomagnetic field. Consequently, basalt core paleomagnetic data are valuable for the constraints they provide on plate tectonic motions, especially for oceanic plates such as the Pacific. Unfortunately, few Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) boreholes have been cored very deeply into the ocean crust. The result is that there are only a few sites at which a large enough number of basalt flows have been cored to properly average secular variation (e.g., Kono, 1980, doi:10.2973/dsdp.proc.55.135.1980; Cox and Gordon, 1984, doi:10.1029/RG022i001p00047). Furthermore, there are a number of sites where basaltic core samples were retrieved but the cores were not measured. Often this occurs because leg scientists had more important sections to work on, or the section was ignored because it was too short to record enough time to average secular variation and obtain a reliable paleolatitude. Even though it may not be possible to determine a precise paleolatitude from such short sections, measurements from a small number of flows are important because they can be combined with other coeval paleomagnetic data from the same plate to calculate a paleomagnetic pole (Gordon and Cox, 1980, doi:10.1111/j.1365-246X.1980.tb02642.x; Cox and Gordon, 1984, doi:10.1029/RG022i001p00047). For this reason, I obtained samples for paleomagnetic measurements from eight Pacific sites (169, 170, 171, 581, 597, 800, 803, and 865), most of which have not been previously measured for paleomagnetism.

Composition of sediments and cores from DSDP Legs 54 and 61-63

The monograph gives results of studies of sediments and rocks collected from D/S Glomar Challenger in the Pacific Ocean. These studies have been based on the lithological facial analysis applied for the first time for identificating genesis of ocean sediments. These results include new ideas on formation of the Earth's sedimentary cover and can be used for constructing regional and global schemes of ocean paleogeography, reconstructing some structures, correlating sedimentation on continents and in oceans, estimating perspectives of oil- and gas-bearing deposits and ore formation. The monograph also gives the first petrographic classification of organic matter in black shales.

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.

Compressional and shear wave velocities and elastic constants at DSDP Leg 59 Holes

Prior to the Deep Sea Drilling Project the composition of the oceanic crust could only be inferred from seismic-refraction and gravity data and the recovery of a wide variety of dredged rocks. Through the success of the Deep Sea Drilling Project, it is now clear that the top of oceanic Layer 2 usually consists of basalt. Several laboratory studies (e.g., Fox et al., 1972; Christensen and Shaw, 1970; Hyndman and Drury, 1976) have demonstrated that the seismic velocities of oceanic basalt are similar to velocities reported from refraction studies of Layer 2 and that the variability in Layer 2 velocities has many causes, the most important being fracturing and sea-floor alteration produced by the interaction of basalt and sea water (Christensen and Salisbury, 1973). To date, most reported measurements of velocities in oceanic basalts are from samples obtained from the main ocean basins. With the exception of an earlier study of velocities and related elastic properties of a suite of rocks from DSDP Sites 292, 293, 294, and 296 located in the Philippine Sea (Christensen et al., 1975; Fountain et al., 1975), elastic properties have not been determined for oceanic rocks from marginal basins. In this chapter compressional- and shear-wave velocities and elastic constants are reported at elevated confining pressures for basalt and volcanic breccias from Holes 447A, 448, and 448A.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Geochemistry of minerals at DSDP Hole 70-504B

Hole 504B, drilled into the 5.9 Ma crust of the southern flank of the Costa Rica Rift, tapped a hydrothermal system in its conductive stage. Three alteration zones were encountered along the 561.5 meters of basement drilled. The upper alteration zone, 274.5 to 584.5 meters below the seafloor (BSF), is characterized by the presence of color zonation in which red halos are located between dark gray inner rock portions and dark gray outer bands. The red halos are characterized by an abundance of iddingsite, and they have higher K2O contents and Fe3+/FeT ratios, but lower SiO2 contents, than the adjacent dark gray inner zones. The dark gray outer bands are characterized by the presence of celadonite-nontronite. Saponite is omnipresent in these three alteration bands. Phillipsite is the only zeolite that occurs in the upper alteration zone. The upper alteration zone is interpreted as being the result of low-temperature alteration, with large amounts of cold oxygenated seawater percolating through the upper ocean crust. In the upper alteration zone, the formation of red halos was both preceded and followed by formation of dark gray outer bands. Then followed formation of dark gray cores. The lower alteration zone (584.5-835.5 m BSF) is characterized by the absence of color zonation, the downward-increasing abundance of pyrite and saponite, and the presence of quartz, talc, and calcite. The chemical changes (downhole MgO enrichment and concomitant CaO depletion) observed in the basalts of the lower alteration zone are thought to result from reactions of oceanic basalts with evolved seawater (i.e., solutions derived from seawater that has already reacted with ocean crust), which is thus depleted in oxygen, potassium, and radiogenic strontium. This alteration process, which was responsible for saponite formation in both the upper and lower alteration zones, was rock dominated, and it took place under suboxic to anoxic conditions during a second stage of alteration. Reaction temperatures could have progressively increased with depth. There is also a zeolitic zone that essentially coincides with the lower part of the upper alteration zone (between 528.5 and 563 m BSF). The host rock adjacent to veins of zeolite exhibits a greenish discoloration due to the intensive replacement of the igneous minerals. The replacement minerals result in significant increases in the bulk rock K2O, MgO, CaO, CO2, and H2O+ contents. The solutions circulating along the newly opened fissures had high Ca activity, and minerals probably precipitated in these fissures at 60°C or 110°C. These hydrothermal solutions circulated later than those responsible for the formation of the minerals that characterize the upper and lower alteration zones.

Pb concentrations, Pb isotopic composition, and amount of metalliferous components in pelagic sediments from the Pacific Ocean

The amount of lead annually transferred from oceanic crust to metalliferous sediments was estimated in order to test the hypothesis that a non-magmatic flux of lead causes the Pb surplus in the continental crust. A Pb surplus has been inferred from global crust-mantle lead mass balances derived from lead concentration correlations with other trace elements and from lead isotope systematics in oceanic basalts. DSDP/ODP data on the amount of metalliferous sediments in the Pacific Ocean and along a South Atlantic traverse are used to calculate the mean worldwide thickness of 3 (+/-1) m for purely metalliferous sediment componens. Lead isotope ratios of 39 metalliferous sediments from the Pacific define mixing lines between continent-derived (seawater) and mantle-derived (basaltic) lead, with the most metal-rich sediments usually having the most mantle-like Pb isotope composition. We used this isotope correlation and the Pb content of the 39 metalliferous sediments to derive an estimate of 130 (+/-70) µg/g for the concentration of mantle-derived lead in the purely metalliferous end-member. Mass balance calculations show that at least 12 (+/-8)% of the lead, annually transferred from upper mantle to oceanic crust at the ocean ridges, is leached out by hydrothermal processes and re-deposited in marine sediments. If all of the metalliferous lead is ultimately transferred to the continental crust during subduction, the annual flux of this lead from mantle to continental crust is 2.6 (+/-2.0) * 10**6 kg. Assuming this transfer rate to be proportional to the rate of oceanic plate production, one can fit the lead transfer to models of plate production rate variations through time. Integrating over 4 Ga, hydrothermal lead transfer to the continental crust accounts for a significant portion of the Pb surplus in the continental crust. It therefore appears to be one of the main reasons for the anomalous behavior of lead in the global crust-mantle system.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

(Table 2) Geochemistry of K-feldspars and associated plagioclase phenocrysts and rims at DSDP Legs 69, 52, 51 and 19

Basalts from some holes of the Deep Sea Drilling Project contain secondary K-feldspar which forms pseudomorphs after calcic (>76% An) Plagioclase cores, whereas Plagioclase of rims and microlites (68-74% An) remains unaltered. In basalts of Hole 504B two such grains with relics of Plagioclase in the central parts of phenocysts were recovered. The composition of the Plagioclase rims and of non-replaced phenocrysts is An79-81; the composition of relics is An83. The An and Ab contents of the K-feldspar is higher than in K-feldspar from altered basalt in Hole 418A in the Atlantic Ocean near the Bermuda Rise. Replacement of plagioclases by K-feldspar evidently is caused by oxygen-rich nearbottom sea water penetrating into basalts. The temperature interval of K-feldspathization is probably in the range 30 to 80°C, more-calcic Plagioclase being replaced by K-feldspar at higher temperatures.

Geochemistry of basement carbonates from ODP Site 801 in the western Pacific Ocean

Many studies argue, based partly on Pb isotopic evidence, that recycled, subducted slabs reside in the mantle source of ocean island basalts (OIB) (Hofmann and White, 1982, doi:10.1016/0012-821X(82)90161-3; Weaver, 1991 doi:10.1016/0012-821X(91)90217-6; Lassiter, and Hauri, 1998, doi:10.1016/S0012-821X(98)00240-4). Such models, however, have remained largely untested against actual subduction zone inputs, due to the scarcity of comprehensive measurements of both radioactive parents (Th and U) and radiogenic daughter (Pb) in altered oceanic crust (AOC). Here, we discuss new, comprehensive measurements of U, Th, and Pb concentrations in the oldest AOC, ODP Site 801, and consider the effect of subducting this crust on the long-term Pb isotope evolution of the mantle. The upper 500 m of AOC at Site 801 shows >4-fold enrichment in U over pristine glass during seafloor alteration, but no net change to Pb or Th. Without subduction zone processing, ancient AOC would evolve to low 208Pb/206Pb compositions unobserved in the modern mantle (Hart and Staudigel, 1989 [Isotopic characterization and identification of recycled components, in: Crust/Mantle Recycling at Convergence Zones, Eds. S.R. Hart, L. Gqlen, NATO ASI Series. Series C: Mathematical and Physical Sciences 258, pp. 15-28, D. Reidel Publishing Company, Dordrecht-Boston, 1989]). Subduction, however, drives U-Th-Pb fractionation as AOC dehydrates in the earth's interior. Pacific arcs define mixing trends requiring 8-fold enrichment in Pb over U in AOC-derived fluid. A mass balance across the Mariana subduction zone shows that 44-75% of Pb but <10% of U is lost from AOC to the arc, and a further 10-23% of Pb and 19-40% of U is lost to the back-arc. Pb is lost shallow and U deep from subducted AOC, which may be a consequence of the stability of phases binding these elements during seafloor alteration: U in carbonate and Pb in sulfides. The upper end of these recycling estimates, which reflect maximum arc and back-arc growth rates, remove enough Pb and U from the slab to enable it to evolve rapidly (<<0.5 Ga) to sources suitable to explain the 208Pb/206Pb isotopic array of OIB, although these conditions fail to simultaneously satisfy the 207Pb/206Pb system. Lower growth rates would require additional U loss (29%) at depths beyond the zones of arc and back-arc magmagenesis, which would decrease upper mantle kappa (232Th/238U) over time, consistent with one solution to the "kappa conundrum" (Elliott et al., 1999, doi:10.1016/S0012-821X(99)00077-1). The net effects of alteration (doubling of l [238U/204Pb]) and subduction (doubling of omega [232Th/204Pb]) are sufficient to create the Pb isotopic signatures of oceanic basalts.

Wet-bulk densities, mean atomic weights, effective porosities, grain densities, and compressional-wave velocities at DSDP Leg 58 Holes

The effects of water saturation and open pore space on the seismic velocities of crystalline rocks are extremely important when comparing laboratory data to in situ geophysical observations (e.g., Dortman and Magid, 1969; Nur and Simmons, 1969; Christensen and Salisbury, 1975). The existence of fractured rocks, flow breccias and drained pillows in oceanic crustal layer 2a, for instance, may appreciably reduce seismic velocities in that layer (Hyndman, 1976). Laboratory data assessing the influence of porosity and water saturation on seismic velocities of oceanic crustal rocks would certainly aid interpretation of marine geophysical data. Igneous rocks recovered during Leg 58 of the Deep Sea Drilling Project, in the Shikoku Basin and Daito Basin in the North Philippine Sea, are extremely vesicular, as evidenced by shipboard measurements of porosities, which range from 0 to 30 per cent (see reports on Sites 442, 443, 444, and 446, this volume). Samples with this range of porosities afford an excellent opportunity to examine the influence of porosity and water saturation on seismic velocities of oceanic basalts. This paper presents compressional-wave velocities to confining pressures of 1.5 kbars for water-saturated and air-dried basalt samples from the North Philippine Sea. Samples used in this study are from sites 442, 443 and 444 in the Shikoku Basin and Site 446 in the Daito Basin. Excellent negative correlation between porosity and compressional-wave velocity demonstrates that waterfilled pore space can significantly reduce compressionalwave velocities in porous basalts. Velocities measured in air-dried samples indicate that the velocity difference between dry samples and saturated samples is small for porosities exceeding 10 per cent, and very large for lower porosities.