Products of chlorophyll diagenesis from DSDP Leg 57 Holes

Tetrapyrrole pigments isolated from sediments retrieved during Leg 57 include pheophytin-a, a myriad of chlorins, free-base deoxophylloerythroetioporphyrin (DPEP), as well as copper and nickel porphyrins. Their richness, both qualitatively and quantitatively, in chlorin tetrapyrroles affords a relatively complete study on the early diagenesis of chlorophyll. Our studies, coupled with those in the preceding chapter by Louda et al., point out the influence of pre- and postdepositional environments upon the mode of chlorophyll diagenesis. Formation of tetrapyrroles, collectively called "petroporphyrins," is seen to occur in only a limited set of environmental conditions (see Baker and Palmer, 1978). The more generalized route of chlorophyll diagenesis, at least in the ocean, results in removal of tetrapyrrole pigment, from the fossil record. Late diagenetic products, metalloporphyrins, are found to represent an extremely minor component of the tetrapyrrole assemblage in sediments studied from the Japan Trench. The products of chlorophyll diagenesis isolated from Japan Trench sediments allow expansion of previous diagenetic schemes (Baker and Palmer, 1978; Triebs, 1936) and indicate directions for future studies.

Organic d13C values, kerogen atomic C/N ratios and relative weights of some kerogen pyrolysis products of ODP Hole 112-682A (Table 1)

Carbon isotopic composition of predominantly marine kerogen in latest Oligocene mudstones of the Peru Margin ODP 682A Hole shows an about 3.5? increase with decreasing age. Py-GC and elemental (C=N ratio) analysis of the kerogen plus sulphur isotopic study together with earlier knowledge on geological setting and organic geochemistry results in a better understanding of depositionary environment and allows to separation of the influence of concentration of water dissolved carbon dioxide (ce) on kerogen delta13C from that of other factors (bacterial degradation, sea surface temperature, DIC delta13C, productivity, and admixture of land plant OM). Based on this analysis, the major part of the kerogen shift is considered as a result of the latest Oligocene decrease of marine photosynthetic carbon isotopic fractionation in the Peru Margin photic zone, which in turn possibly reflects a simultaneous drop in atmospheric CO2 level. Uncertainties in the evaluation of the factors affecting the marine photosynthetic carbon isotopic fractionation and the extent of ocean-atmosphere disequilibrium do not permit calculation of the decrease of the atmospheric CO2.

Mineralogy and geochemistry of alteration products in DSDP Leg 81 Holes

Alteration products of basalts from the four holes drilled during Leg 81 were studied and found to be characterized by the widespread occurrence of trioctahedral clay minerals (Mg smectite to chlorite). In some cases zeolites (analcite, chabazite) are associated with the saponite. A more oxidizing stage is marked by a saponite-celadonite association, presenting the geochemical characteristics of hydrothermal processes. Later stages of alteration are represented by palagonitization and subaerial weathering at two sites. These different alteration processes of basalts from Leg 81 record the paleoenvironment during the first opening stages of the Northeast Atlantic Ocean in the Paleocene-Eocene periods.

Isotope ratios of basalts from ODP Leg 115 holes (Table 1)

Strontium, neodymium, and lead isotope ratios are reported for 13 Leg 115 basalts as well as 3 basalts from Texaco drill hole SM-1 on the Mascarene Plateau. The 87Sr/86Sr ratios and eNd range from 0.70330 to 0.70439 and 5.5 to 7.4, respectively, although 87Sr/86Sr ratios higher than 0.70383 are found only in SM-1 basalts. The high 87Sr/86Sr values are thought to reflect seawater Sr in secondary phases, although all samples were strongly leached in HC1 before analysis. 206Pb/204Pb ratios range from 18.53 to 18.80, and sho high 207Pb/204Pb and 208Pb/204Pb ratios relative to 206Pb/204Pb ratios, typical of Indian Ocean mid-ocean ridge (MORB) and oceanic-island basalts (OIB). Isotopic compositions of Leg 115 basalts generally fall between fields for MORB and Reunion Island basalts, consistent with the conclusion drawn from geochronological studies that Deccan flood basalt volcanism, the Chagos-Laccadive Ridge, and the Mascarene Plateau are all products of the Reunion mantle plume. Isotopic compositions of magmas produced by this plume have varied systematically with time in the direction of less "depleted," less MORB-like isotopic signatures. This compositional change has been accompanied by a decrease in eruption rate. We interpret Deccan volcanism as the voluminous beginning of the plume. Reduced entrainment of asthenosphere following melting of the plume head resulted in less MORB-like isotope ratios in magmas and a decrease in eruptive activity with time.

(Table 1) Isotopic composition of Sm and Nd in mantle restites of the Central Atlantic and in associated plutonic and volcanic rocks

Ultrabasic rock samples collected from two areas of the crustal zone of the Mid-Atlantic Ridge (MAR): (1) 13-17°N (near the intersection of the ridge axis with the 15°20'N prime fracture zone), and (2) 33°40'N prime (the western intersection of the MAR crest with the Heis fracture zone) were objects of this study. Samples of peridotite and of plutonic and volcanic rocks associated with it were used to measure their Sm/Nd, 143Nd/144Nd, and 147Sm/144Nd ratios, which allowed to test time and genetic relationships between evolution of mantle material under the ridge crest and products of its magmatic activity. Results of this work proved ubiquitous discrepancy between melting degree values of extremely depleted mantle peridotites in the MAR area between 14°N and 16°N, obtained using petrologic and geochemical methods. This discrepancy suggests large-scale interaction between mantle material and magmatic melts and fluids enriched in incompatible elements or fluids. The results obtained suggest that repeated melting of the mantle under the axial MAR zone is an universal characteristic of magmatism in low-velocity spreading centers. The results of this study also proved the crestal MAR zone in the Central Atlantic region show distinct indications of isotope-geochemical segmentation of the mantle. It is suggested that the geochemically anomalous MAR mantle peridotite in the zone of the MAR intersection with the 15°20'N prime fracture zone can be interpreted as fragments of mantle substrate, foreign for the Atlantic mantle north of the equator.

Composition of chromian diopside megacryst in DSDP Leg 37 basalts (Table 2, 3)

Refractory megacrysts of olivine, plagioclase, chromian diopside and Cr-Al spinel, which were not in equilibrium with the host oceanic tholeiite on eruption, are present in samples from several dredge sites and DSDP drill sites in the Atlantic and Pacific Oceans. They have multiple origins: (1) cognate or accidental mantle fragments; (2) relict fragments from fractional crystallization of parental liquids considerably more primitive than oceanic tholeiite; and most commonly (3) the fractional crystallization products of such liquids mixed with oceanic tholeiite magma. Melt inclusions in chrome-spinel phenocrysts provide evidence for this postulated Mg- and Ca-rich magma which has counterparts in the Scottish Tertiary Province and in west Greenland.