Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Oxygen, hydrogen, and carbon isotopic compositions in deep sea cherts, porcellanites, and coexisting carbonates from DSDP Legs 2, 3, 6, 7, 11, 14, 16, 17, and 20

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. d18O of chert ranges between 27 and 39%. relative to SMOW, d18O of porcellanite - between 30 and 42%. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases. d18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975; http://www.deepseadrilling.org/32/volume/dsdp32_15.pdf) indicates the possibility of d18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of d18O values, increasing diagenesis being reflected in a lowering of d18O. Drusy quartz has the lowest d18O values. On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts. Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. dD of this water ranges between -78 and -95%. and is not a function of d18O of the cherts (or the temperature of their formation).

Secondary minerals and geochemistry in basalts at DSDP Leg 67 Legs

Secondary minerals in basalts from Holes 495 and 500 include smectite and chlorite, both of which have partially replaced the basalt groundmass. In addition to these two minerals, amphibole, laumontite, albite, and a corrensitelike mineral are present in Holes 499B and 499C. Smectite, chlorite, talc, calcite, phillipsite, mica, and mixed-layer chlorite-montmorillonite also fill veins in the basalts of Hole 495. The secondary mineral assemblages from Site 499 are characteristic of the initial stage of greenschist facies metamorphism.

Geochemistry of carbon at DSDP Legs 56-57 Holes

Forty-three core sections from Sites 434, 435, 438, 439, and 440 on the landward side and six core sections from Site 436 on the seaward side of the Japan Trench were obtained through the JOIDES Organic Geochemistry Advisory Panel for study of the origin and state of genesis of the organic matter associated with these continental slope, accretionary wedge, and outer trench slope sediments of the Japan Trench. The lipid fraction of these sediments is derived primarily from terrigenous organic matter and thus is allochthonous to the area. The associated kerogen fraction is of mixed allochthonous and autochthonous origin. The total organic carbon content seaward of the trench is less than that on the landward side. The composition of this organic matter is similar but not identical to that found in the landward side sediments. The organic matter within these sediments is in a diagenetic state in which geopolymerization of biogenic organic matter is nearly complete, but microbial alteration is still occurring.

Trace element abundances and Sr and Nd isotope compositions in bulk sediments from DSDP Legs 6 and 20

Rare earth element and Nd isotopic data for ten representative samples of Lower Cretaceous to Miocene pelagic sediments from the western Pacific indicate a wide range of compositions for sediments being subducted beneath the Mariana and Volcano arcs. All samples are enriched in light rare earth elements and show negative Eu and Ce anomalies. The values of e-Nd range from +0.6 to -7.3. These data are used to calculate the Bulk Western Pacific Sediment (BWPS), which is characterized by low Sr/Nd (10), Ba/La (13), and e-Nd (-5.2) and high 87Sr/86Sr (0.7078) compared to that of Mariana and Volcano arc lavas. This composite sediment is used to refine a mixing model for the origin of Mariana and Volcano arc melts. Some lavas from the northern Mariana Arc have Ba/La higher than that of BWPS, which indicates that a third component is required. The high Ba/La in the mantle source for these lavas is interpreted to result from multiple episodes of fluid fractionation. The mixing model indicates that a minor amount of sediment and a low proportion of metasomatic fluid fluxes the mantle source at a late stage when the subarc mantle is already highly metasomatized. This model also suggests that the mantle source for arc melts is affected more by metasomatic fluids than by melting or bulk mixing of sediments.

Secondary minerals and geochemistry at DSDP Legs 68 and 69

Basalt samples recovered during DSDP Legs 68, 69, and 70 from a 550-meter-thick section in two holes near the Costa Rica Rift (Holes 501 and 504B) were found to contain the following secondary minerals: trioctahedral and dioctahedral smectite, chlorite, mixed-layer clays, talc, hematite, pyrite, foujasite, phillipsite, analcime, natrolite, thomsonite, gyrolite, aragonite, calcite, anhydrite, chalcocite, Fe-hydrosilicate, okenite, apophyllite, actinolite, cristobalite, quartz, and magnesite. A less positive identification of bismutite was made. A mineral rich in Mn and minerals with strong reflections at 12.9 Å and 3.20 Å remain unidentified. Trioctahedral smectite replaces glass and olivine in the basalt groundmass. The other secondary minerals occur in veins. The distribution of the secondary minerals in the basalt section shows both hydrothermal and oxidizing-nonoxidizing zonation. Most of the secondary minerals formed under alkaline, nonoxidizing conditions at temperatures up to 120° C. An acidic regime probably existed in the lowest portion of basalt. Oxidative diagenesis followed nonoxidative diagenesis in the upper part of the section. Oxidative diagenesis is characterized by the absence of celadonite, rare occurrences of dioctahedral smectite, and widespread hematite and phillipsite.

Rhenium and platinum-group element concentrations and Os isotope data for Philippine Sea Plate basalts from DSDP Legs 31, 58, and 59

Platinum-group elements (PGE), rhenium and osmium isotope data are reported for basalts from Deep Sea Drilling Project cores in the Philippine Sea Plate (PSP). Lithophile trace element and isotopic characteristics indicate a range of source components including DMM, EMII and subduction-enriched mantle. MORB-like basalts possess smooth, inclined chondrite-normalised PGE patterns with high palladium-PGE/iridium-PGE ratios, consistent with previously published data for MORB, and with the inferred compatibility of PGE. In contrast, while basalts with EMII-type lithophile element chemistry possess high Pt/Ir ratios, many have much lower Pd/Ir and unusually high Ru/Ir of >10. Similarly, back-arc samples from the Shikoku and Parece-Vela basins have very high Ru/Ir ratios (>30) and Pd/Ir as low as 1.1. Such extreme Pd/Ir and Ru/Ir ratios have not been previously reported in mafic volcanic suites and cannot be easily explained by variable degrees of melting, fractional crystallisation or by a shallow-level process such as alteration or degassing. The data appear most consistent with sampling of at least two mantle components with distinct PGE compositions. Peridotites with the required PGE characteristics (i.e. low Pd, but relatively high Ru and Re) have not been documented in oceanic mantle, but have been found in sub-continental mantle lithosphere and are the result of considerable melt depletion and selective metasomatic enrichment (mainly Re). The long-term presence of subduction zones surrounding the Philippine Sea Plate makes this a prime location for metasomatic enrichment of mantle, either through fluid enrichment or infiltration by small melt fractions. The Re-Os isotope data are difficult to interpret with confidence due to low Os concentrations in most samples and the uncertainty in sample age. Data for Site 444A (Shikoku Basin) give an age of 17.7+/-1.3 Ma (MSWD = 14), consistent with the proposed age of basement at the site and thus provides the first robust radiometric age for these samples. The initial 187Os/188Os of 0.1298+/-0.0069 is consistent with global MORB, and precludes significant metasomatic enrichment of Os by radiogenic slab fluids. Re-Os data for Sites 446A (two suites, Daito Basin) and 450 (Parece-Vela Basin) indicate ages of 73, 68 and 43 Ma, which are respectively, 30, 17 and >12 Ma older than previously proposed ages. The alkalic and tholeiitic suites from Site 446A define regression lines with different 187Os/188Osinitial (0.170+/-0.033 and 0.112+/-0.024, respectively) which could perhaps be explained by preferential sampling of interstitial, metasomatic sulphides (with higher time-integrated Re/Os ratios) by smaller percentage alkalic melts. One sample, with lithophile elements indistinguishable from MORB, is Os-rich (146 pg/g) and has an initial 187Os/188Os of 0.1594, which is at the upper limit of the accepted OIB range. Given the Os-rich nature of this sample and the lack of evidence for subduction or recycled crust inputs, this osmium isotope ratio likely reflects heterogeneity in the DMM. The dataset as a whole is a striking indication of the possible PGE and Os isotope variability within a region of mantle that has experienced a complex tectonic history.

Isotopic composition of rocks from the Lau/Tonga back-arc basin, data of DSDP Leg 21 and ODP Legs 91 an 135

New trace element, Sr-, Nd-, Pb- and Hf isotope data provide insights into the evolution of the Tonga-Lau Basin subduction system. The involvement of two separate mantle domains, namely Pacific MORB mantle in the pre-rift and early stages of back-arc basin formation, and Indian MORB mantle in the later stages, is confirmed by these results. Contrary to models proposed in recent studies on the basis of Pb isotope and other compositional data, this change in mantle wedge character best explains the shift in the isotopic composition, particularly 143Nd/144Nd ratios, of modern Tofua Arc magmas relative to all other arc products from this region. Nevertheless, significant changes in the slab-derived flux during the evolution of the arc system are also required to explain second order variations in magma chemistry. In this region, the slab-derived flux is dominated by fluid; however, these fluids carry Pb with sediment-influenced isotopic signatures, indicating that their source is not restricted to the subducting altered mafic oceanic crust. This has been the case from the earliest magmatic activity in the arc (Eocene) until the present time, with the exception of two periods of magmatic activity recorded in samples from the Lau Islands. Both the Lau Volcanic Group, and Korobasaga Volcanic Group lavas preserve trace element and isotope evidence for a contribution from subducted sediment that was not transported as a fluid, but possibly in the form of a melt. This component shares similarities with that influencing the chemistry of the northern Tofua Arc magmas, suggesting some caution may be required in the adoption of constraints for the latter dependent upon the involvement of sediments from the Louisville Ridge. A key outcome of this study is to demonstrate that the models proposed to explain subduction zone magmatism cannot afford to ignore the small but important contributions made by the mantle wedge to the incompatible trace element inventory of arc magmas.

Silicic tephras in ODP Legs 151, 152, and 162

A 6-m.y.-long composite marine record of explosive silicic volcanism from five Ocean Drilling Program sites in the subpolar North Atlantic was compared with several marine records of global and local paleoclimate proxies (benthic d18O and ice-rafted debris records). Coarsening and high frequency of occurrence of Icelandic tephras were recorded in 3.6-3 Ma sediments, suggesting that these tephras were dispersed farther from the source by enhanced westerly winds over the subpolar North Atlantic. The 40Ar/39Ar ages were determined by laser probe on K-feldspar and biotite phenocrysts of tephras that were erupted from the Jan Mayen volcanic system. Compared to the tuned paleomagnetic age model, the 40Ar/39Ar dating (0.618+/-0.007 Ma to 4.90+/-0.05 Ma) yields a new age model that postdates by 155 k.y. the inception of ice rafting on the Iceland Plateau during the cold marine isotope stage M2 (i.e., 3.3-3.14 Ma).

Basalt density, basement age, and intrusive/extrusive relations from DSDP Legs 2 through 7, 9, and 14

Densities of layer 2 basalt recovered during the Deep Sea Drilling Project have been found to decrease steadily with age, a finding ascribed to progressive submarine weathering in the context of sea-floor spreading. The least-squares solution for 52 density measurements gives a rate of decrease in density of (Delta p)/(Delta t) = -0.0046 g per ccm m.y. = -16 percent per 100 m.y., which is in excellent agreement with earlier estimates based on observed chemical depletion rates of dredged oceanic basalt. Weathering of sea-floor basalt, should it penetrate to any considerable depth in layer 2, will decrease layer 2 seismic refraction velocities, act as a source of geothermal heat, and substantially influence the chemistry of sea water and the overlying column of sediment.

(Table 1) Heavy minerals at DSDP Legs 56-57 Holes

Heavy-mineral assemblages in the cored sediments from DSDP Legs 56 and 57 show a distinct change of source rocks, from older sedimentary rocks during the Oligocene to volcanic rocks during the Miocene through Pleistocene. The former might have been supplied by the "Oyashio ancient landmass," and the latter from the volcanic areas in Hokkaido and northeast Honshu. This indicates a shift of the Japanese Islands toward the continent.