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.

Geochemical records of sediment cores from the Sea of Japan

Intervals of organic C- and carbonate-rich laminated sediments occur in the Sea of Japan with roughly the same frequency as temperature changes observed in Greenland ice cores, providing clear evidence of rapid oceanographic change during the past 36 kyr. Planktonic foraminiferal d18O data suggest that only the laminated sediments deposited during the Last Glacial Maximum (LGM), and perhaps one other interval formed during a period of increased water column stratification. Sedimentary Re and Mo data are consistent with bottom waters that were sulfidic during the LGM and suboxic during other laminated intervals. Results of a numerical model of Corg and Re burial are consistent with a mechanism whereby an increased Corg flux to the seafloor drove oxygen concentrations toward depletion during times of deposition of the suboxic laminated intervals. Such a process could have resulted from increased upwelling driven either by increased deep water formation due to colder and/or more saline surface waters or by stronger northeasterly monsoonal winds.

Age determination of sediment cores of the California Current System

Alkenone sea surface temperature (SST) records were generated from the Ocean Drilling Program's (ODP) Sites 1014 and 1016 to examine the response of the California Current System to global climate change during the last 136 ka. The temperature differences between these sites (Delta SST(NEP)=SST(ODP1014)-SST(ODP1016)) reflected the intensity of the California Current and varied between 0.4 and 6.1 °C. A high Delta SST(NEP) (weaker California Current) was found for late marine isotope stage (MIS) 2 and early MIS 5e, while a low Delta SST(NEP) (stronger California Current) was detected for mid-MIS 5e and MIS 1. Spectral analysis indicated that this variation pattern dominated 23- (precession) and 30-ka periods. Comparison of the Delta SST(NEP) and SST based on data from core MD01-2421 at the Japan margin revealed anti-phase variation; the high Delta SST(NEP) (weakening of the California Current) corresponded to the low SST at the Japan margin (the southward displacement of the NW Pacific subarctic boundary), and vice versa. This variation was synchronous with a model prediction of the tropical El Niño-Southern Oscillation behavior. These findings suggest that the intensity of the North Pacific High varied in response to precessional forcing, and also that the response has been linked with the changes of tropical ocean-atmosphere interactions.

Calculated surface water paleotemperatures for the lower Pliocene at DSDP Site 18-173 from the California continental slope (Table I)

The oxygen isotope record of the planktonic foraminifera Globigerina bulloides and Neogloboquadrina pachyderma from Pliocene and early Pleistocene sediments at both DSDP site 173 and the Centerville Beach section in California suggests a large influx of isotopically light water in this area during late Pliocene and early Pleistocene time. Salinity may have been reduced by as much as 2 to 4 ?. Surface sea water paleotemperatures for the lower Pliocene range from 9.5°C to 15.5°C. The oxygen isotope record of the benthonic genus Uvigerina shows little variation indicating environmental stability at depth. At DSDP site 173 the small variation in Uvigerina is due to variation in the oxygen isotopic composition of the oceans as glaciers waxed and waned. At the Centerville Beach section the oxygen isotopic composition of Uvigerina reflects the gradual shoaling of the Humboldt Basin. Carbon and oxygen isotope ratios in G. bulloides and N. pachyderma are inversely correlated at the 95% confidence level. This may indicate that the oxygen and carbon isotopic composition of foraminifera are influenced by the same factors. On the other hand, the inverse correlation may be due to metabolic fractionation. No correlation was found between oxygen and carbon isotopic composition in Uvigerina.

Sea surface temperature reconstruction of sediment profile W8709A-8

Assessment of changes in surface ocean conditions, in particular, sea-surface temperature (SST), is essential to understand long-term changes in climate especially in regions where continental climate is strongly influenced by oceanographic processes. To evaluate changes in SST in the northeast Pacific, we have analyzed long-chain alkenones of prymnesiophyte origin at 38 depths in a piston and associated trigger core collected beneath the contemporary core of the California Current System at 42°N, ~270 km off the coast of Oregon/California. The samples span 30,000 years of deposition at this location. Unsaturation patterns (UK'37) in the alkenone series display a statistically significant difference (p <<0.001) between interglacial (0.44 ± 0.02, n = 11) and glacial (0.29 ± 0.04, n = 20) intervals of the cores. Detailed examination of other compositional features of the C37, C38, C39 alkenone series and a related C36 alkenoate series measured downcore suggests the published UK'37 - temperature calibration (UK'37 = 0.034 * T + 0.039 ) , defined for cultures of a strain of Emiliania huxleyi isolated from the subarctic Pacific, provides best estimates of winter SST at our study site. This inference is purely statistical and does not imply, however, that the phytoplankton source of these biomarkers is most productive in winter or at the ocean surface. The temperature record for UK'37 implies (1) an ~4°C shift occurred in winter SST from ~7.5 ± 1.1°C at the last glacial maximum to ~11.7 ± 0.7°C in the present interglacial period, and (2) this warming trend was confined to the time frame 14-10 Ka within the glacial to interglacial transition period. These conclusions are corroborated entirely by results from an independent SST transformation of radiolarian species assemblage data obtained from the same core materials.