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.

Pliocene foraminifera and SST changes in ODP Site 184-1125

Planktonic foraminiferal census counts were converted to sea surface temperature (SST) estimates using the modern analogue technique (MAT) for the middle-late Pliocene (4.0-2.37 Ma) in ODP Site 1125, north side of Chatham Rise, SW Pacific Ocean. MAT SST(warm) records range between 8°C and 20.5°C, and MAT SST(cold) records parallel that pattern but with a temperature range of 5-15°C. The modern position of Site 1125 is just north of the Subtropical Front and has an annual temperature range of ~14-18°C. Pliocene warmest temperatures are 1-2° warmer than modern summers, whereas cold season SST records are up to 6-10°C cooler than modern winters. Overall average temperatures at the site are 2-3°C cooler than modern temperatures during a time of sustained global warmth. Three major cold excursions centred on 3.35, 3.0, and 2.8 Ma showed warm season temperatures over 5°C colder than the last glacial maximum, experiencing temperatures typical of modern subantarctic waters. Two minor cold excursions at 2.7 Ma and 2.4 Ma experienced temperatures cooler than modern winters but not as cold as last glacial conditions. Cold season SSTs show a shift to warmer climate upward through the study interval, whereas warm season estimates remain essentially unchanged. We interpret the strong regional cooling of subtropical Southwest Pacific water through the middle-late Pliocene as having been caused by increased upwelling. It is also possible that the subtropical frontal zone moved north over the site in the Pliocene, however, this is considered the least likely interpretation. Our record of cool conditions in the Southwest Pacific corroborate evidence of cooler than modern conditions in other regions of the western Pacific through the mid-Pliocene despite overall global warming.

Cd and d13C reconstruction for the LGM and Holocene in Brazil Margin sediment cores

Paleoceanographic studies using benthic foraminiferal Cd as a nutrient tracer have provided a robust means of reconstructing glacial Atlantic Ocean water mass geometry, but a paucity of data from the South Atlantic above 1200 m has limited investigation of Antarctic Intermediate Water (AAIW) configuration and formation. A new Cd depth profile from Brazil margin sediments suggests that AAIW penetrated northward at 1100 m to at least 27°S in the glacial Atlantic. It exhibited substantially reduced d13Cas values, confirming preliminary evidence that this AAIW was unique to the glacial Atlantic and that it formed differently than today, with less atmospheric contact.

Seawater Cd reconstruction for the western subtropical South Atlantic

Benthic foraminiferal Cd/Ca from an intermediate depth, western South Atlantic core documents the history of southward penetration of North Atlantic Intermediate Water (NAIW). Cd seawater estimates (CdW) for the last glacial are consistent with the production of NAIW and its export into the South Atlantic. At ~14.5 ka concurrently with the onset of the Bølling-Allerød to Younger Dryas cooling, the NAIW contribution to the South Atlantic began to decrease, marking the transition from a glacial circulation pattern to a Younger Dryas circulation. High CdW in both the deep North Atlantic and the intermediate South Atlantic imply reduced export of deep and intermediate water during the Younger Dryas and a significant decrease in northward oceanic heat transport. A modern circulation was achieved at ~9 ka, concurrently with the establishment of Holocene warmth in the North Atlantic region, further supporting a close linkage between deepwater variability and North Atlantic climate.

Highly dealkylated copper and nickel etioporpyfrins in marine sediments

Copper porphyrins have been recognized as natural constituents of marine sediments only within the past 5 years (Palmer and Baker, 1978, Science201, 49-51). In that report it was suggested that these pigments may derive from and be markers for oxidized terrestrial organic matter redeposited in the marine environment. In the present study we describe the distribution of copper porphyrins in sediments from several north Pacific and Gulf of California DSDP/IPQD sites (Legs 56,63,64). These allochthonous pigments have now been found to be accompanied by identical arrays of highly dealkylated nickel etioporphyrins. Evaluation of data from this and past studies clearly reveals that there is a strong carbon-number distribution similarity betweeen coincident Cu and Ni etioporphyrins. This homology match is taken as reflecting a common source for the tetrapyrrole ligands of this population of Cu and Ni chelates. Predepositional generation of these highly dealkylated etioporphyrins is concluded from the occurrence of these pigments in sediments continuing essentially all stages of in situ chlorophyll diagenesis (cf. Baker and Louda, 1983). That is, their presence is not regulated by the in situ diagenetic continuum. Thus, the highly dealkylated Cu and Ni etioporphyrins represent an 'allochthonous' background over which 'autochthonous' (viz. marine produced) chlorophyll derivatives are deposited and are undergoing in situ diagenesis.

Stable isotope ratios of benthic foraminifera in mid-Pleitsocene sediments of ODP Site 108-664 in the equatorial Atlantic

Five delta13C records from the deep ocean, extending back to 1.3 Ma, were examined in order to constrain changes in mean ocean carbon isotope composition and thermohaline circulation over the 41- to 100-ka climate transition. These data show that significant perturbations in mean ocean carbon chemistry were associated with the mid-Pleistocene climate transition. Notable features of the last 1.3 Myr are (1) a pronounced ~0.3? decrease in mean ocean delta13C between 0.9 and 1.0 Myr, followed by a return to pre-1.0 Ma values by 400 ka B.P., which we propose was due to the onetime addition of isotopically depleted terrestrial carbon to the ocean, possibly associated with an increase in global aridity (and decrease in the size of the biosphere) across the 41- to 100-ka transition; (2) no change in the Atlantic-Pacific (A-P) delta13C gradient over the last 1.3 Myr, suggesting no change in mean ocean nutrient content accompanied the addition of light carbon; and (3) stronger vertical nutrient fractionation in the North Atlantic in the middle Pleistocene between sites 607 and 552, suggesting weaker North Atlantic Deep Water formation at this time relative to the early and late Pleistocene. We also find evidence for a more pronounced deep recirculation gyre in the western North Atlantic basin in the early Brunhes, as evidenced by "aging" of deep northern basin water (site 607) relative to deep water in the equatorial Atlantic (site 664).

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.