Lipid analytic of environmental and cultural samples

Membrane lipids of marine planktonic archaea have provided unique insights into archaeal ecology and paleoceanography. However, past studies of archaeal lipids in suspended particulate matter (SPM) and sediments mainly focused on a small class of fully saturated glycerol dibiphytanyl glycerol tetraether (GDGT) homologues identified decades ago. The apparent low structural diversity of GDGTs is in strong contrast to the high diversity of metabolism and taxonomy among planktonic archaea. Furthermore, adaptation of archaeal lipids in the deep ocean remains poorly constrained. We report the archaeal lipidome in SPM from diverse oceanic regimes. We extend the known inventory of planktonic archaeal lipids to include numerous unsaturated archaeal ether lipids (uns-AELs). We further reveal i) different thermal regulations and polar headgroup compositions of membrane lipids between the epipelagic (<= 100 m) and deep (> 100 m) populations of archaea; ii) stratification of unsaturated GDGTs with varying redox conditions; and iii) enrichment of tetra-unsaturated archaeol and fully saturated GDGTs in epipelagic and deep oxygenated waters, respectively. Such stratified lipid patterns are consistent with the typical distribution of archaeal phylotypes in marine environments. We thus provide an ecological context for GDGT-based paleoclimatology and bring about the potential use of uns-AELs as biomarkers for planktonic Euryarchaeota. This article is protected by copyright. All rights reserved.

Long-term biogenic particle fluxes in the Bering Sea and the central subarctic Pacific Ocean

Time-series sediment traps were deployed for five consecutive years in two distinctively different subarctic marine environments. The centrally located subarctic pelagic Station SA (49°N, 174°W; water depth 5406 m) was simultaneously studied along with the marginal sea Station AB (53.5°N, 177°W; water depth 3788 m) in the Aleutian Basin of the Bering Sea. A mooring system was tethered to the sea-floor with a PARFLUX type trap with 13 sample bottles, which was placed at 600 m above the sea-floor at each of the two stations. Sampling intervals were synchronized at the stations, and they were generally set for 20 days during highly productive seasons, spring through fall, and 56 days during winter months of low productivity. Total mass fluxes, which consisted of mainly biogenic phases, were significantly greater at the marginal sea Station AB than at the pelagic Station SA for the first four years and moderately greater for the last year of the observations. This reflects the generally recognized higher productivity in the Bering Sea. Temporal excursion patterns of the mass fluxes at the two stations generally were in parallel, implying that temporal changes in their biological productivity are strongly governed by a large-scale seasonal climatic variability over the region rather than local phenomena. The primary reason for the difference in total mass flux at the two stations stems mainly from varying contributions of siliceous and calcareous planktonic assemblages. A significantly higher opal contribution at Station AB than at Station SA was mainly due to diatoms. Diatom fluxes at the marginal sea station were about twice those observed at the pelagic station, resulting in a very high opal contribution at Station AB. In contrast to the opal fluxes, CaCO3 fluxes at Station AB were slightly lower than at Station SA. The ratios of Corg/Cinorg were usually significantly greater than one in both regions, suggesting that preferentially greater organic carbon from cytoplasm than skeletal inorganic carbon was exported from the surface layers. Such a process, known as the biological pump, leads to a carbon sink which effectively lowers p CO2 in the surface layers and then allows a net flux of atmospheric CO2 into the surface layer. The efficiency of the biological pump is greater in the Bering Sea than at the open-ocean station.

Magnetic analyses of ODP Hole 119-738B sediments

Magnetotactic bacteria intracellularly biomineralize magnetite of an ideal grain size for recording palaeomagnetic signals. However, bacterial magnetite has only been reported in a few pre-Quaternary records because progressive burial into anoxic diagenetic environments causes its dissolution. Deep-sea carbonate sequences provide optimal environments for preserving bacterial magnetite due to low rates of organic carbon burial and expanded pore-water redox zonations. Such sequences often do not become anoxic for tens to hundreds of metres below the seafloor. Nevertheless, the biogeochemical factors that control magnetotactic bacterial populations in such settings are not well known. We document the preservation of bacterial magnetite, which dominates the palaeomagnetic signal throughout Eocene pelagic carbonates from the southern Kerguelen Plateau, Southern Ocean. We provide evidence that iron fertilization, associated with increased aeolian dust flux, resulted in surface water eutrophication in the late Eocene that controlled bacterial magnetite abundance via export of organic carbon to the seafloor. Increased flux of aeolian iron-bearing phases also delivered iron to the seafloor, some of which became bioavailable through iron reduction. Our results suggest that magnetotactic bacterial populations in pelagic settings depend crucially on particulate iron and organic carbon delivery to the seafloor.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

The SUGAR Toolbox - Version 7

The SUGAR Toolbox contains scripts coded in MATLAB for calculating various thermodynamic, kinetic, and geologic properties of substances occurring in the marine environment, particularly gas hydrate and seep systems. Brief descriptions of the toolbox scripts and some notes on the underlying basic theory as well as tables of additional property values can be found in the accompanying documentation.

(Table 1) Sediment properties at DSDP Leg 67 Holes

The plasticity characteristics of the Quaternary sediments of the Guatemalan continental margin were determined from five sites drilled during Leg 67 of the Deep Sea Drilling Project. The 64 samples analyzed are from various marine environments, including the Cocos Plate, Middle America Trench, and the trench lower slope to midslope of the Guatemalan continental slope. The sediments are primarily hemipelagic muds and trench-fill turbidites and include quantities of siliceous and calcareous biogenic components. The sediments are generally classified as organic clays of medium to high plasticity, containing micaceous sands and silts, with 14% classed as inorganic clays of medium to high plasticity. High sedimentation rates in Quaternary sediments are the result, in part, of sediment gravity flows that depend upon rheological properties, i.e., sediment plasticity. Mudflows and cohesive debris flows appear to be significant downslope transport mechanisms in these highly plastic sediments.

Carbon and Sulphur concentrations of sediments from Peru, Oman and Benguela upwelling environments

Abundances of organic carbon, sulfur, and reactive iron in sediments of three upwelling environments (Peru, Oman and Benguela) suggest that organic carbon/reduced sulfur ratios (C/S-ratios) in this category of marine sediments deviate considerably from previously established empirical ratios in normal marine sediments. To clarify the discrepancies, we investigated those components of the diagenetic system that limit the formation of pyrite: sulfate concentrations and reduction rates in pore waters, availability of reactive iron, and the quantity and quality of organic matter. All three limitations are evident in our sample pools. The results suggest that C/S-ratios in recent and fossil marine sediments rich in organic matter may be unsuitable as paleoenvironmental indicators.

Marine and terrigenous lipids in ODP Leg 175 holes

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 175 in the eastern South Atlantic reflect a variety of oceanographic and climatological environments. Most of the identified lipids can be ascribed to marine sources, notably haptophytes, eustigmatophytes, dinoflagellates, archaea, and diatoms. Elevated concentrations of cholesterol suggest zooplankton herbivory, characteristic for sites influenced by upwelling. At these sites, sulfurized highly branched isoprenoids from diatoms are also present in high amounts. Sterols, sterol ethers, hopanoids, and midchain hydroxy fatty acids could also be detected. Terrigenous lipids are n-alkanes, fatty acids, n-alcohols, and triterpenoid compounds like taraxerol and -amyrine. n-Alkanes, fatty acids, and n-alcohols are derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Triterpenoid compounds are most probably derived from mangroves and transported solely by rivers. Lipid compositions below the Congo low-salinity plume are strongly influenced by terrigenous material from the Congo River. Elevated organic carbon contents and predominantly marine lipid distributions at the Angola margin may indicate a highly productive plankton population, probably sustained by the Angola Dome. Sedimentary lipids in the Walvis Basin contain an upwelling signal, likely transported by the Benguela Current. Sedimentary lipids off Lüderitz Bay and in the southern Cape Basin are dominated by plankton lipids in high to intermediate amounts, reflecting persistent and seasonal upwelling, respectively.

Magnetic susceptibility and electric conductivity of marine surficial sediments by benthic electromagnetic profiling

Distribution, accumulation and diagenesis of surficial sediments in coastal and continental shelf systems follow complex chains of localized processes and form deposits of great spatial variability. Given the environmental and economic relevance of ocean margins, there is growing need for innovative geophysical exploration methods to characterize seafloor sediments by more than acoustic properties. A newly conceptualized benthic profiling and data processing approach based on controlled source electromagnetic (CSEM) imaging permits to coevally quantify the magnetic susceptibility and the electric conductivity of shallow marine deposits. The two physical properties differ fundamentally insofar as magnetic susceptibility mostly assesses solid particle characteristics such as terrigenous or iron mineral content, redox state and contamination level, while electric conductivity primarily relates to the fluid-filled pore space and detects salinity, porosity and grain-size variations. We develop and validate a layered half-space inversion algorithm for submarine multifrequency CSEM with concentric sensor configuration. Guided by results of modeling, we modified a commercial land CSEM sensor for submarine application, which was mounted into a nonconductive and nonmagnetic bottom-towed sled. This benthic EM profiler Neridis II achieves 25 soundings/second at 3-4 knots over continuous profiles of up to hundred kilometers. Magnetic susceptibility is determined from the 75 Hz in-phase response (90% signal originates from the top 50 cm), while electric conductivity is derived from the 5 kHz out-of-phase (quadrature) component (90% signal from the top 92 cm). Exemplary survey data from the north-west Iberian margin underline the excellent sensitivity, functionality and robustness of the system in littoral (~0-50 m) and neritic (~50-300 m) environments. Susceptibility vs. porosity cross-plots successfully identify known lithofacies units and their transitions. All presently available data indicate an eminent potential of CSEM profiling for assessing the complex distribution of shallow marine surficial sediments and for revealing climatic, hydrodynamic, diagenetic and anthropogenic factors governing their formation.

Stable isotope ratios in shells of marine organisms

Oxygen and carbon isotope analyses have been carried out on calcareous skeletons of important recent groups of organisms. Annual temperature ranges and distinct developmental stages can be reconstructed from single shells with the aid of the micro-sampling technique made possible by modern mass-spectrometers. This is in contrast to the results of earlier studies which used bulk sampIes. The skeletons analysed are from Bermuda, the Philippines, the Persian Gulf and the continental margin off Peru. In these environments, seasonal salinity ranges and thus annual variations in the isotopic composition of the water are small. In addition, environmental parameters are weIl documented in these areas. The recognition of seasonal isotopic variations is dependant on the type of calcification. Shells built up by carbonate deposition at the margin, such as molluscs, are suitable for isotopic studies. Analysis is more difficult where chambers are added at the margin of the shell but where older chambers are simultaneously covered by a thin veneer of carbonate e. g. in rotaliid foraminifera. Organisms such as calcareous algae or echinoderms that thicken existing calcareous parts as weIl as growing in length and breadth are the most difficult to analyse. All organisms analysed show temperature related oxygen-isotope fractionation. The most recent groups fractionate oxygen isotopes in accordance with established d18O temperature relationships (Tab. 18, Fig. 42). These groups are deep-sea foraminifera, planktonic foraminifera, serpulids, brachiopods, bryozoa, almost all molluscs, sea urchins, and fish (otoliths). A second group of organisms including the calcareous algae Padina, Acetabularia, and Penicillus, as weIl as barnacles, cause enrichment of the heavy isotope 18O. Finally, the calcareous algae Amphiroa, Cymopolia and Halimeda, the larger foraminifera, corals, starfish, and holothurians cause enrichment of the lighter isotope 16O. Organisms causing non-equilibrium fractionation also record seasonal temperature variations within their skeletons which are reflected in stable-oxygen-isotope patterns. With the exception of the green algae Halimeda and Penicillus, all organisms analysed show lower d13C values than calculated equilibrium values (Tab. 18, Fig. 42). Especially enriched with the lighter isotope 12C are animals such as hermatypic corals and larger foraminifera which exist in symbiosis with other organisms, but also ahermatypic corals, starfish, and holothurians. With increasing age of the organisms, seven different d13C trends were observed within the skeletons. 1) No d13C variations are observed in deep-sea foraminifera presumably due to relatively stable environmental conditions. 2) Lower d13C values occur in miliolid larger foraminifera and are possibly related to increased growth with increasing age of the foraminifera. 3) Higher values are found in planktonic foraminifera and rotaliid larger foraminifera and can be explained by a slowing down of growth with increasing age. 4) A sudden change to lower d13C values at a distinct shell size occurs in molluscs and is possibly caused by the first reproductive event. 5) A low-high-Iow cycle in calcareous algae is possibly caused by variations in the stage of calcification or growth. 6) A positive correlation between d18O and d13C values is found in some hermatypic corals, all ahermatypic corals, in the septa of Nautilus and in the otoliths of fish. In hermatypic corals from tropical areas, this correlation is the result of the inverse relationship between temperature and light caused by summer cloud cover; in other groups it is inferred to be due to metabolic processes. 7) A negative correlation between d18O and d13C values found in hermatypic corals from the subtropics is explained by the sympathetic relationship between temperature and light in these latitudes. These trends show that the carbon isotope fractionation is controlled by the biology of the respective carbonate producing organisms. Thus, the carbon isotope distribution can provide information on the symbiont-host relationship, on metabolic processes and calcification and growth stages during ontogenesis of calcareous marine organisms.

Stratigraphic occurrence of selected marine palynomorph species recorder in the Paleogene of ODP Hole 105-647A (Table 3)

Dinoflagellate cysts were recovered throughout the Paleogene succession of Hole 647A, which contains an almost complete deep-water record of early Eocene through early late Oligocene sedimentation in the Labrador Sea. Dinoflagellate cyst biostratigraphy is in general accord with that provided by other microfossil groups and is consistent with a lower Eocene age, as determined by nannofossils, for basal sediments in Hole 647A. These sediments overlie oceanic crust of Chron 24 age. Dinocyst assemblages indicate outer neritic to oceanic conditions throughout, although the persistent occurrence of Wetzeliellaceae specimens in the lower Eocene suggests a greater influence from shelf environments during this time. Lower Eocene dinocyst assemblages are similar to coeval assemblages from the Rockall Plateau, but those from the middle to upper Eocene have mixed affinities and may be related to the intensification of the proto-Gulf Stream from middle Eocene time. Oligocene dinocyst assemblages suggest the influence of both arctic and North Atlantic wate rmasses at this site. The presence of protoperidineacean species in the upper Eocene and Oligocene may indicate increased availability of nutrients, perhaps related to increased upwelling or the effects of water-mass mixing. Productive samples are dominated by dinocysts and acritarchs, while sporomorphs are represented mainly by bisaccate pollen. Preservational differences within samples may reflect mixing of penecontemporaneous dinocyst populations during the Eocene, and all samples examined may have a considerable allochthonous component. Variability in relative abundance of many species during the Eocene may be related to fluctuating water-mass properties. A total 175 dinocyst and acritarch taxa were recorded from 53 productive samples from the Paleogene. Only one Paleogene sample was barren of palynomorphs. Of three Miocene samples processed, all were barren.

Major, trace element and XRF data for sediments and fish tooth samples, from a shallow marine setting with varying redox conditions (Site U1356, Wilkes Land Margin, E.Antarctica)

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

Climate sensitivity across marine domains of life: limits to evolutionary adaptation shape species interactions, supplementary material

Organisms in all domains, Archaea, Bacteria, and Eukarya will respond to climate change with differential vulnerabilities resulting in shifts in species distribution, coexistence, and interactions. The identification of unifying principles of organism functioning across all domains would facilitate a cause and effect understanding of such changes and their implications for ecosystem shifts. For example, the functional specialization of all organisms in limited temperature ranges leads us to ask for unifying functional reasons. Organisms also specialize in either anoxic or various oxygen ranges, with animals and plants depending on high oxygen levels. Here, we identify thermal ranges, heat limits of growth, and critically low (hypoxic) oxygen concentrations as proxies of tolerance in a meta-analysis of data available for marine organisms, with special reference to domain-specific limits. For an explanation of the patterns and differences observed, we define and quantify a proxy for organismic complexity across species from all domains. Rising complexity causes heat (and hypoxia) tolerances to decrease from Archaea to Bacteria to uni- and then multicellular Eukarya. Within and across domains, taxon-specific tolerance limits likely reflect ultimate evolutionary limits of its species to acclimatization and adaptation. We hypothesize that rising taxon-specific complexities in structure and function constrain organisms to narrower environmental ranges. Low complexity as in Archaea and some Bacteria provide life options in extreme environments. In the warmest oceans, temperature maxima reach and will surpass the permanent limits to the existence of multicellular animals, plants and unicellular phytoplankter. Smaller, less complex unicellular Eukarya, Bacteria, and Archaea will thus benefit and predominate even more in a future, warmer, and hypoxic ocean.

Diversity of ocean acidification effects on marine N2 fixers

Considering the important role of N2 fixation for primary productivity and CO2 sequestration, it is crucial to assess the response of diazotrophs to ocean acidification. Previous studies on the genus Trichodesmium suggested a strong sensitivity towards ocean acidification. In view of the large functional diversity in N2 fixers, the objective of this study was to improve our knowledge of the CO2 responses of other diazotrophs. To this end, the single-celled Cyanothece sp. and two heterocystous species, Nodularia spumigena and the symbiotic Calothrix rhizosoleniae, were acclimated to two pCO2 levels (380 vs. 980 µatm). Growth rates, cellular composition (carbon, nitrogen and chlorophyll a) as well as carbon and N2 fixation rates (14C incorporation, acetylene reduction) were measured and compared to literature data on different N2 fixers. The three species investigated in this study responded differently to elevated pCO2, showing enhanced, decreased as well as unaltered growth and production rates. For instance, Cyanothece increased production rates with pCO2, which is in line with the general view that N2 fixers benefit from ocean acidification. Due to lowered growth and production of Nodularia, nitrogen input to the Baltic Sea might decrease in the future. In Calothrix, no significant changes in growth or production could be observed, even though N2 fixation was stimulated under elevated pCO2. Reviewing literature data confirmed a large variability in CO2 sensitivity across diazotrophs. The contrasting response patterns in our and previous studies were discussed with regard to the carbonate chemistry in the respective natural habitats, the mode of N2 fixation as well as differences in cellular energy limitation between the species. The group-specific CO2 sensitivities will impact differently on future biogeochemical cycles of open-ocean environments and systems like the Baltic Sea and should therefore be considered in models estimating climate feedback effects.