Geochemistry and stable isotopes of peridotites of ODP Hole 103-637A

A ridge of strongly serpentinized, plagioclase-bearing peridotite crops out at the boundary between the Atlantic oceanic crust and the Galicia continental margin (western Spain). These peridotites, cored at Hole 637A (ODP Leg 103) have been mylonitized at high-temperature, low-pressure conditions and under large deviatoric stress during their uplift (Girardeau et al., 1988, doi:10.2973/odp.proc.sr.103.135.1988). After this main ductile deformation event, the peridotite underwent a polyphase metamorphic static episode in the presence of water, with the crystallization of Ti- and Cr-rich pargasites at high-temperature (800°-900°C) interaction with a metasomatic fluid or alkaline magma. Introduction of water produced destabilization of the pyroxenes and the subsequent development of hornblendes and tremolite at temperatures decreasing from 750° to 350°C. The main serpentinization of the peridotite occurred at a temperature below 300°C, and possibly around 50°C, as a consequence of the introduction of a large amount of seawater, which is suggested by stable isotope (d18O and SD) data. Finally, calcite derived from seawater precipitated in late-formed fractures or locally pervasively impregnated the peridotite at low temperature (~10°C).

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

Primary mineralogy of ODP Leg 115 basalts

Basement rocks were recovered at four sites on Leg 115 along the Reunion hotspot track in the western Indian Ocean. Plate tectonic reconstructions indicate that the drilled structures formed in three different volcanic environments. Sites 706 and 713 from the eastern side of the Saya de Malha Bank and the northern end of the Chagos Bank, respectively, are on a large volcanic platform analogous to Iceland on the Mid-Atlantic Ridge. Lavas at Site 707 on the northwestern side of the Saya de Malha Bank erupted during the early stages of rifting of the Seychelles from India. Basalts from Site 715 were erupted onto an isolated oceanic island that was distant from ocean ridges and continents much as Reunion Island is today. Many of the rocks were examined in thin section and found to be primarily augite-plagioclase basalts with minor olivine and rare opaque oxides. Site 715 is unusual in that it contains a variety of basalts including olivine-rich and aphyric Fe-Ti basalts. At each of the four sites the rocks were grouped into chemical types (units) on the basis of ship- board bulk-rock analyses and at least one thin section from each chemical unit was analyzed by electron microprobe. The plagioclase and augite chemistry reflects the bulk-rock chemistry and, in general, these minerals were in equilibrium with their host magmas at the time the basalts were quenched. Olivine was rarely preserved, but where it is still present it also appears to have crystallized in equilibrium with the host magma. At three of the drill sites plagioclase phenocrysts or megacrysts that crystallized from a primitive magma are also present. The one site (715) that does not contain these primitive plagioclase phenocrysts is also the site that appears to have been influenced the least by ocean- ridge or Deccan-type magmas. Site 715, furthermore, has a mineralogy that is dominated by olivine as compared with the plagioclase-rich lavas of the other sites.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Geochemistry of ODP Leg 125 peridotites

Trace element analyses (first-series transition elements, Ti, Rb, Sr, Zr, Y, Nb, and REE) were carried out on whole rocks and minerals from 10 peridotite samples from both Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc using a combination of XRF, ID-MS, ICP-MS, and ion microprobe. The concentrations of incompatible trace elements are generally low, reflecting the highly residual nature of the peridotites and their low clinopyroxene content (<2%). Chondrite-normalized REE patterns show extreme U shapes with (La/Sm)n ratios in the range of 5.03-250.0 and (Sm/Yb)n ratios in the range of 0.05-0.25; several samples show possible small positive Eu anomalies. LREE enrichment is common to both seamounts, although the peridotites from Conical Seamount have higher (La/Ce)n ratios on extended chondrite-normalized plots, in which both REEs and other trace elements are organized according to their incompatibility with respect to a harzburgitic mantle. Comparison with abyssal peridotite patterns suggests that the LREEs, Rb, Nb, Sr, Sm, and Eu are all enriched in the Leg 125 peridotites, but Ti and the HREEs exhibit no obvious enrichment. The peridotites also give positive anomalies for Zr and Sr relative to their neighboring REEs. Covariation diagrams based on clinopyroxene data show that Ti and the HREEs plot on an extension of an abyssal peridotite trend to more residual compositions. However, the LREEs, Rb, Sr, Sm, and Eu are displaced off this trend toward higher values, suggesting that these elements were introduced during an enrichment event. The axis of dispersion on these plots further suggests that enrichment took place during or after melting and thus was not a characteristic of the lithosphere before subduction. Compared with boninites sampled from the Izu-Bonin-Mariana forearc, the peridotites are significantly more enriched in LREEs. Modeling of the melting process indicates that if they represent the most depleted residues of the melting events that generated forearc boninites they must have experienced subsolidus enrichment in these elements, as well as in Rb, Sr, Zr, Nb, Sm, and Eu. The lack of any correlation with the degree of serpentinization suggests that low-temperature fluids were not the prime cause of enrichment. The enrichment in the high-field-strength elements also suggests that at least some of this enrichment may have involved melts rather than aqueous fluids. Moreover, the presence of the hydrous minerals magnesio-hornblende and tremolite and the common resorption of orthopyroxene indicate that this high-temperature peridotite-fluid interaction may have taken place in a water-rich environment in the forearc following the melting event that produced the boninites. The peridotites from Leg 125 may therefore contain a record of an important flux of elements into the mantle wedge during the initial formation of forearc lithosphere. Ophiolitic peridotites with these characteristics have not yet been reported, perhaps because the precise equivalents to the serpentinite seamounts have not been analyzed.

Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.

Pebbles and carbonate nodules Legs 56-57 Holes

At all DSDP Leg 56 drilling sites, exotic pebbles occur commonly, throughout the cores. Chips of carbonate nodules occur only at Site 434 on the lower inner trench wall. Both exotic pebbles and carbonate nodule chips sometimes tend to be concentrated at particular levels of cores. Exotic pebbles are generally well rounded and consist of various rock types, such as dacite, andesite, basalt, tuff, gabbro, granodiorite, metaquartzite, biotite hornfels, lithic wacke, mudstone, etc., of which dacite occurs commonly at all the sites. Almost all pebbles at Site 436 and most at Sites 434 and 435 may have been rafted by ice. Some at the latter sites may have been derived by down-slope slumping. Carbonate nodules consist of microcrystalline dolomite, manganoan calcite, and siderite; CaCO3 content ranges from 22 to 65 per cent. They are also generally characterized by a high content of P2O5. The nodules are commonly rich in diatom remains, some of which indicate that the nodules are autochthonous. Some nodules contain abundant glass shards, with a modal refractive index of 1.499, almost identical to shards in the surrounding mud and ooze. These facts suggest that the carbonate nodules may have been formed diagenetically, in situ. This may throw light on problems of the formation of carbonate nodules in ancient "geosynclinal" sediments. It is also very important to point out that these carbonate nodules were formed within sediment deposited well below the CCD.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Contents of major and noble chemical elements in phosphorites and bottom sediments

Ag and Au are typically concentrated in phosphorites; they genetically related to organic matter of bottom sediments that extract these elements from seawater or interstitial water. Consequently, the phosphorites inherit Ag and Au from host sediments that are not always enriched in them. In contrast to other organic-rich sediments, analyzed sample of recent diatom ooze from the Namibian shelf is not enriched in Ag and Au, although some sediments from this region are enriched in Au. In addition to authigenic Au, allochthonous Au associated with quartz grains and micrograins can also be present in shelf phosphorites. This was observed in oceanic phosphorites of various types. Anomalous Au and Fe contents recorded in one seamount phosphorite sample can be related to extraction of Au and nonferrous metals by ferromanganese hydroxides from seawater. This process can serve as one of major mechanisms of Au supply to ferromanganese crusts on seamounts. Phosphorites and sediments are enriched in Ru simultaneously with U. Author's data show that U content varies from 17 (seamount phosphorite) to 887 ppm (Pleistocene phosphorite nodule from the Namibian shelf). This is probably caused by different types of behavior of light and heavy PGEs in the marine environment.