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.

Foraminiferal species and dissolution index at DSDP Hole 78-541

The calcite compensation depth (CCD) fluctuates as a result of changes in the water-mass system, thereby producing a distinct dissolution pattern. Differential dissolution changes the composition of the foraminiferal assemblages, reflecting the depositional environment in respect to the fluctuating CCD. The dissolution pattern for the comparatively shallow Site 541 on the Barbados Ridge indicates a depositional environment mostly above the CCD, but below the foraminiferal lysocline during the late Miocene to early Pleistocene. In contrast, sediments of the deeper-water Site 543 indicate a depositional environment above the CCD during the late Pliocene to early Pleistocene only. Furthermore, similarities in the dissolution pattern of corresponding time intervals of Site 541 (represented by superimposed faulted intervals termed Tectonic Units A and B) are recognizable. Sediments deposited clearly above the foraminiferal lysocline are rare

Interstitial water chemistry at DSDP Leg 82 Holes

Interstitial waters were collected at only two sites during Leg 82, Sites 558 and 563. Only very small changes in dissolved calcium and magnesium occur, presumably resulting from reactions in the underlying basement basalts. Dissolved strontium profiles indicate maxima, which can be understood in terms of carbonate recrystallization processes. Data on Sr/Ca in carbonates cannot be used to estimate the extent of recrystallization that has occurred in these sediments.

Organic geochemistry of sediments at DSDP Leg 63 Holes

Selected core samples from the California Continental Borderland (Sites 467-469) were analyzed to evaluate the nature and composition of the lipids and kerogens in terms of their genetic origin and geological maturity. The lipids were of a multiple origin. On the basis of the homolog distributions of the n-alkanes and n-fatty acids, with the shape and magnitude of the unresolved branched and cyclic hydrocarbons, and the structural and stereochemical compositions of the molecular markers, these lipids were derived from primary autochthonous marine (microbial), from allochthonous terrigenous (higher plant wax), and from recycled (geologically mature organic matter) sources. The kerogens were composed of principally marine microbial detritus with a minor input of allochthonous terrestrial material. For the most part, the samples had undergone a thermal maturation according to a normal geothermal gradient, except in the proximity of intrusives. Such additional thermal stress was evident for the samples from Site 469 and to some extent for Site 467 at about a sub-bottom depth of 700 to 800 meters.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

Maxima of interstitial water and gas parameters in ODP Leg 182 sediments

During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106?) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200-400 m) and relative warm bottom water temperatures (11-14°C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant (SO4)2- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

Maastrichtian planktic foraminifera of the South Atlantic Ocean

Stratigraphic, faunal and isotopic analyses of the Maastrichtian at DSDP sites 525A and 21 in the South Atlantic reveal a planktic foraminiferal fauna characterized by two major events, an early late Maastrichtian diversification and end-Maastrichtian mass extinction. Both events are accompanied by major changes in climate and productivity. The diversification event which occurred in two steps between 70.5 and 69.1 Ma increased species richness by a total of 43% and coincided with the onset of major cooling in surface and bottom waters and increased surface productivity. The onset of the terminal decline in Maastrichtian species richness began at 67.5 Ma and the first significant decline in surface productivity occurred at 66.2 Ma, coincident maximum cooling to 13°C in surface waters and the reduction of the surface-to-deep temperature gradient to less than 5°C. Major climatic and moderate productivity changes mark the mass extinction and the last 500 kyr of the Maastrichtian. Between 200 and 400 kyr before the K-T boundary surface and deep waters warmed rapidly by 3-4°C and cooled again during the last 100 kyr of the Maastrichtian. Surface productivity decreased only moderately across the K-T boundary. Species richness began to decline during the late Maastrichtian cooling and by K-T boundary time, the mass extinction had claimed 66% of the species. Viewed within the context of Maastrichtian climate and productivity changes, the K-T mass extinction could have resulted from extreme environmental stress even without the addition of an extraterrestrial impact.

Characterization of late Campanian and Maastrichtian planktonic foraminiferal depth habitats and vital activities based on stable isotopes

Depth habitats of 56 late Cretaceous planktonic foraminiferal species from cool and warm climate modes were determined based on stable isotope analyses of deep-sea samples from the equatorial Pacific DSDP Sites 577A and 463, and South Atlantic DSDP Site 525A. The following conclusions can be reached: Planoglobulina multicamerata (De Klasz) and Heterohelix rajagopalani (Govindan) occupied the deepest plankton habitats, followed by Abathomphalus mayaroensis (Bolli), Globotruncanella havanensis (Voorwijk), Gublerina cuvillieri Kikoine, and Laeviheterohelix glabrans (Cushman) also at subthermocline depth. Most keeled globotruncanids, and possibly Globigerinelliodes and Racemiguembelina species, lived at or within the thermocline layer. Heterohelix globulosa (Ehrenberg) and Rugoglobigerina, Pseudotextularia and Planoglobulina occupied the subsurface depth of the mixed layer, and Pseudoguembelina species inhabited the surface mixed layer. However, depth ranking of some species varied depending on warm or cool climate modes, and late Campanian or Maastrichtian age. For example, most keeled globotruncanids occupied similar shallow subsurface habitats as Rugoglobigerina during the warm late Campanian, but occupied the deeper thermocline layer during cool climatic intervals. Two distinct types of "vital effect" mechanisms reflecting photosymbiosis and respiration effects can be recognized by the exceptional delta13C signals of some species. (1) Photosymbiosis is implied by the repetitive pattern of relatively enriched delta13C values of Racemiguembelina (strongest), Planoglobulina, Rosita and Rugoglobigerina species, Pseudoguembelina excolata (weakest). (2) Enriched respiration 12C products are recognized in A. mayaroensis, Gublerina acuta De Klasz, and Heterohelix planata (Cushman). Isotopic trends between samples suggest that photosymbiotic activities varied between localities or during different climate modes, and may have ceased under certain environmental conditions. The appearance of most photosymbiotic species in the late Maastrichtian suggests oligotrophic conditions associated with increased water-mass stratification.

Radiolaria abundance and faunal indices of ODP Hole 183-1138A, Kerguelen Plateau

Three sites from Ocean Drilling Program (ODP) Leg 183 (Kerguelen Plateau) have been analyzed to document faunal change in high-latitude radiolarians and to compare the faunal change to Eocene-Oligocene climatic deterioration. Radiolarians are not preserved in Eocene sediments. In Oligocene sediments, radiolarian preservation improves in a stepwise manner toward the Miocene. A total of 115 species were found in lower Oligocene samples from Site 1138; all are documented herein. Radiolarian preservation is presumably linked to productivity triggered by climatic cooling during the early Oligocene. Similar patterns of improving preservation through the Eocene/Oligocene boundary are documented from several Deep Sea Drilling Project and ODP sites in the Southern Ocean, indicating a general pattern. In contrast to the Southern Kerguelen Plateau, however, proxies for productivity are more divergent at Site 1138 (Central Kerguelen Plateau). Whereas carbonate dissolution, as indicated by poor preservation of foraminifers and common hiatuses, is very pronounced in the upper Eocene-lowermost Oligocene, the quality of radiolarian and diatom preservation does not significantly increase until the uppermost lower Oligocene. Multiple measures of radiolarian diversity in the Oligocene from Site 1138 closely parallel radiolarian preservation, indicating that preserved radiolarian diversity is controlled by productivity.

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.