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.

Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.

Oxygen and carbon isotopic composition in Eocene and Oligocene planktonic and benthic foraminifera from DSDP sediments

Oxygen and carbon isotope ratios in Eocene and Oligocene planktonic and benthic foraminifera have been investigated from Atlantic, Indian, and Pacific Ocean locations. The major changes in Eocene-Oligocene benthic foraminiferal oxygen isotopes were enrichment of up to 1 per mil in 18O associated with the middle/late Eocene boundary and the Eocene/Oligocene boundary at locations which range from 1- to 4-km paleodepth. Although the synchronous Eocene-Oligocene 18O enrichment began in the latest Eocene, most of the change occurred in the earliest Oligocene. The earliest Oligocene enrichment in 18O is always larger in benthic foraminifera than in surface-dwelling planktonic foraminifera, a condition that indicates a combination of deep-water cooling and increased ice volume. Planktonic foraminiferal d18O does not increase across the middle/late Eocene boundary at our one site with the most complete record (Deep Sea Drilling Project Site 363, Walvis Ridge). This pattern suggests that benthic foraminiferal d18O increased 40 m.y. ago because of increased density of deep waters, probably as a result of cooling, although glaciation cannot be ruled out without more data. Stable isotope data are averaged for late Eocene and earliest Oligocene time intervals to evaluate paleoceanographic change. Average d18O of benthic foraminifera increased by 0.64 per mil from the late Eocene to the early Oligocene d18O maximum, whereas the average increase for planktonic foraminifera was 0.52 per mil. This similarity suggests that the Eocene/Oligocene boundary d18O increase was caused primarily by increased continental glaciation, coupled with deep sea cooling by as much as 2°C at some sites. Average d18O of surface-dwelling planktonic foraminifera from 14 upper Eocene and 17 lower Oligocene locations, when plotted versus paleo-latitude, reveals no change in the latitudinal d18O gradient. The Oligocene data are offset by ~0.45 per mil, also believed to reflect increased continental glaciation. At present, there are too few deep sea sequences from high latitude locations to resolve an increase in the oceanic temperature gradient from Eocene to Oligocene time using oxygen isotopes.

Stable carbon and oxygen isotope ratios of Late Miocene and Early Pliocene foraminifera from the Southwest Pacific

The Late Miocene-Early Pliocene paleoclimatic history has been evaluated for a deep drilled sediment sequence at Deep Sea Drilling Project Site 281 and a shallow water marine sediment sequence at Blind River, New Zealand, both of which lay within the Subantarctic water mass during the Late Miocene. A major, faunally determined, cooling event within the latest Miocene at Site 281 and Blind River coincides with oxygen isotopic changes in benthonic foraminiferal composition at DSDP Site 284 considered by Shackleton and Kennett (1975) to indicate a significant increase in Antarctic ice sheet volume. However, at Site 281 benthonic foraminiferal oxygen isotopic changes do not record such a large increase in Antarctic ice volume. It is possible that the critical interval is within an unsampled section (no recovery) in the latest Miocene. Two benthonic oxygen isotopic events in the Late Miocene (0.5 ? and 1 ? in the light direction) may be useful as time-stratigraphic markers. A permanent, negative, carbon isotopic shift at both Site 281 and Blind River allows precise correlations to be made between the two sections and to other sites in the Pacific region. Close interval sampling below the carbon shift at Site 281 revealed dramatic fluctuations in surface-water temperatures prior to a latest Miocene interval of refrigeration (Kapitean) and a strong pulse of dissolution between 6.6 and 6.2 +/- 0.1 m.y. which may be related to a fundamental geochemical change in the oceans at the time of the carbon shift (6.3-6.2 m.y.). No similar close interval sampling at Blind River was possible because of a lack of outcrop over the critical interval. Paleoclimatic histories from the two sections are very similar. Surface water temperatures and Antarctic ice-cap volume appear to have been relatively stable during the late Middle-early Late Miocene (early-late Tongaporutuan). By 6.4 m.y. cooler conditions prevailed at Site 281. Between 6.3 and 6.2 -+ 0.1 m.y. the carbon isotopic shift occurred followed, within 100,000 yr, by a distinct shallowing of water depths at Blind River. The earliest Pliocene (Opoitian) is marked by increasing surface-water temperatures.

Quaternary surface-water stable isotope signal from calcareous nannofossils at DSDP Site 90-593, South Tasman Sea

Oxygen isotope values from calcareous nannofossils in four cores spanning the Quaternary from DSDP Site 593 in Tasman Sea are compared with the delta18O signal of planktonic and benthic foraminifers from the same samples. The classic mid-late Quaternary isotope stages are exhibited with stage 12 particularly well developed. When delta18O values of nannofossils are adjusted for coccolithophore vital effects they indicate larger (by 1-6°C) surface to bottom paleotemperature gradients and greater (by 1-3°C) changes in mean sea-surface temperature between full glacial and interglacial conditions than do delta18O values from planktonic foraminifers. Along with the foraminifers, the nannofossils record a bimodal distribution of delta18O between the early and mid-late Quaternary, indicating a significant change in global ice budget. The delta13C of nannofossils also shows a bimodal distribution, but is opposite to that for the foraminifers. Nannofossil delta18O values record a shift of c. -0.8? at isotope stage 8 corresponding to a major reduction in abundance of the previously dominant gephyrocapsids. A shift in delta13C of c. -1.5? also occurs at stage 8, and a shift in delta13C of c. +1.2? at around stage 14. The delta18O shift in nannofossils is at least a Pacific-wide phenomenon; the delta13C shifts are possibly global. The delta13C signal of nannofossils exhibits an antipathetic relationship to that of benthic foraminifers back to isotope stage 18 but no significant correlation beyond this level to the base of the Quaternary. This is interpreted as reflecting local productivity dominating global influences on delta13C since stage 18 at DSDP Site 593. The difference between nannofossil and benthic foraminifer delta13C signals (Delta13C) tends to be maximum during glacial stages and minimum during interglacials throughout the section, showing a strong correlation with the nannofossil delta180 signal. The increased partitioning of 13C between surface and bottom waters during the glacial periods may indicate heightened productivity in surface waters in the southern Tasman Sea at these times.

Stable oxygen isotope record and age determination of sediments from the North Atlantic Ocean

Sea surface temperature and salinity estimates reconstructed using planktonic foraminiferal abundance and delta18O records from core SU90-03 (40°N, 32°W, 2475 m water depth) reveal large climatic fluctuations linked to major instabilities in Northern Hemisphere ice sheets over the last 150 000 years. Episodes of enhanced ice rafted detritus (IRD) input were accompanied by discrete temperature minima, representing coolings of between 4 and 8°C, and reductions in surface salinity of up to 2.5-3.5 per mil. Several additional cooling episodes of a similar magnitude were documented during intervals of low IRD input that appear to be synchronous, within the limits of dating, with ice rafting events spatially confined to higher latitudes. Accelerator mass spectrometer 14C dates for Heinrich events (H1 - 14.2 ka, H2 - 21.4 ka, H3 - 26.7 ka, H4 - 34.8 ka, H5 - 47.2 ka) obtained from core SU90-03 agree well with other published age estimates and suggest a contemporaneous pattern of climate change throughout the North Atlantic during the last glacial period. This interpretation is supported by a comparison of IRD and palaeotemperature records from DSDP site 609 and core SU90-03, which clearly shows that the major climatic fluctuations identified at high latitudes were transmitted toward the subtropics. However, 14C dates suggest that ice rafting episodes may be diachronous to some extent. The northward migration of the polar front after the H1 event at 40°N in the mid-Atlantic occurred at 14 ka, approximately 500 years earlier than along the Portuguese margin, where the southerly advection of polar waters persisted within eastern boundary current system.

Oxygen and carbon isotopes for foraminifers at DSDP Leg 73 Holes

We carried out oxygen and carbon isotope studies on monospecific foraminifer samples from DSDP Sites 522, 523, and 524 of Leg 73 in the central South Atlantic Ocean. The oxygen isotope ratios show a warming of 2 to 3 °C in bottom water and 5°C in surface water during the Paleocene and early Eocene. The carbon isotope values indicate strong upwelling during the early Eocene. The 1% increase in the d18O values of benthic and planktonic foraminifers at Site 523 in the later middle Eocene we ascribe to changes in the pattern of the evaporation and precipitation. The changes may be due to the worldwide Lutetian transgression. The oxygen ratios for the benthic and planktonic foraminifers indicate a cooling at the Eocene/Oligocene transition. The maximum temperature drop (5°C for benthic and 3°C for planktonic foraminifers) is recorded slightly beyond the Eocene/Oligocene boundary and took place over an interval of about 100,000 yr. The pattern of currents in the Southern Hemisphere was mainly structured by a precursor of the subtropical convergence during the Paleocene to late Eocene. The cooling at the Eocene/Oligocene transition led to drastic changes in the circulation pattern, and a precursor of the Antarctic convergence evolved.

Osmium, and stable carbon and oxygen isotope record accross the PETM

In the latest Paleocene an abrupt shift to more negative d13C values has been documented at numerous marine and terrestrial sites (Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Cramer et al., 1999; Kaiho et al., 1996, doi:10.1029/96PA01021; Kennett and Stott, 1991, doi:10.1038/353225a0; Koch et al., 1992, doi:10.1038/358319a0; Stott et al., 1996; Thomas and Shackleton, 1996, doi:10.1144/GSL.SP.1996.101.01.20; Zachos et al., 1993). This carbon isotope event (CIE) is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4°-6°C (Kennett and Stott, 1991, doi:10.1038/353225a0) and more moderate warming in the subtropics (Thomas et al., 1999, doi:10.1029/1999PA900031). Here we report 187Os/188Os isotope records from the North Atlantic and Indian Oceans which demonstrate a >10% increase in the 187Os/188Os ratio of seawater coincident with the late Paleocene CIE. This excursion to higher 187Os/188Os ratios is consistent with a global increase in weathering rates. The inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate, which acts to stabilize Earth's climate (Walker et al., 1981). Estimates of the duration of late Paleocene CIE (Bains et al., 1999, doi:10.1126/science.285.5428.724; Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Norris and Röhl, 1999, doi:10.1038/44545; Röhl et al., 2000, doi:10.1130/0091-7613(2000)28<927:NCFTLP>2.0.CO;2) in conjunction with the Os isotope data imply that intensified chemical weathering in response to warm, humid climates can occur on timescales of 104-105 years. This interpretation requires that the late Paleocene thermal maximum Os isotope excursion be produced mainly by increased Os flux to the ocean rather than a transient excursion to higher 187Os/188Os ratios in river runoff. Although we argue that the former is more likely than the latter, we cannot rule out significant changes in the 187Os/188Os ratio of rivers.

Stable oxygen and carbon isotope composition of benthic foraminifera from the western Mediterranean Sea

The influence of microhabitat, organic matter flux, and metabolism on the stable oxygen and carbon isotope composition of live (Rose Bengal stained) and dead (empty tests) deep-sea benthic foraminifera from the Gulf of Lions (western Mediterranean Sea) have been studied. The total range of observed foraminiferal isotope values exceeds 1.0 per mil for d18O and 2.2 per mil for d13C demonstrating a wide range of coexisting disequilibria relative to d18O of equilibrium calcite (d18OEQ) and d13C of bottom water dissolved inorganic carbon (d13CDIC). The mean d18O values reveal strongest disequilibria for the studied epifaunal to shallow infaunal species (Cibicidoides pachydermus, Uvigerina mediterranea, Uvigerina peregrina) while values approach equilibrium in deep infaunal species (Globobulimina affinis, Globobulimina pseudospinescens). The mean d13C values decrease with increasing average living depths of the different species, thus reflecting a dominant microhabitat (pore water) signal. At the axis of the Lacaze-Duthier Canyon a minimum d13CDIC pore water gradient of approximately -2.1 per mil is assessed for the upper 6 cm of the surface sediment. Although live individuals of U. mediterranea were found in different depth intervals their mean d13C values are consistent with calcification at an average living depth around 1 cm. The deep infaunal occurrence of U. mediterranea specimens suggests association with macrofaunal burrows creating a microenvironment with geochemical characteristics similar to the topmost centimeter. This also explains the excellent agreement between stable isotope signals of live and dead individuals. The ontogenetic enrichment in both d18O and d13C values of U. mediterranea suggests a slow-down of metabolic rates during test growth similar to that previously observed in planktic foraminifera. Enhanced organic carbon fluxes and higher proportion of resuspended terrestrial organic material at the canyon axis are reflected by d13C values of U. mediterranea on average 0.58 per mil lower than those from the open slope. These results demonstrate the general applicability of the d13C signal of this species for the reconstruction of past organic matter fluxes in the Mediterranean Sea. Further studies on live specimens are needed for a more quantitative paleoceanographic approach.

Live benthic foraminifera in surface sediments of the Indo-Pakistan continental margin

The Indo-Pakistan Continental Margin represents an extreme habitat for benthic foraminifera since (1) high fluxes of organic matter offer a high food supply, (2) an intensified oxygen minimum Zone (OMZ) develops from the base of the euphotic Zone to water depths over 1000 m and (3) the monsoon causes seasonal oscillations within the biogeochemical cycle. At three stations from the uppermost (233 m), the central (658 m) and the deeper part (902 m) of the OMZ, living benthic foraminiferal assemblages were analyzed within the uppermost 10 cm of the sediment column. The ecologic structure of foraminiferal faunas is characterized by high abundances at the sediment surface and a rapid decrease within the uppermost 2 cm of the sediment column. Despite dysoxic to suboxic bottom-water conditions, stained benthic foraminifera occurred in all cores down to the base of the sampled interval. High surface abundances, a high dominance by few endobenthic calcareous taxa and a low diversity, which may result from specific physiological adaptations to almost anoxic conditions and the absence of predators, are recognized in the central part of the OMZ. The upper and lower margins of the OMZ are characterized by higher diversities and lower abundances. The shallowest part of the OMZ is dominated by calcareous foraminifera, whereas agglutinated species are the most common taxa in the deeper part. Comparisons with previous studies show that benthic foraminiferal assemblages, that are influenced by seasonal oscillations controlling food supply and/or the availability of oxygen, show variations in faunal density and species composition. Since there is strong evidence that oxygen is not a limiting factor for some taxa, it seems more likely that the distribution pattern of benthic foraminifera is preferentially controlled by trophic conditions.

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.