Isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) at different cold seep provinces

Anaerobic methane-oxidizing microbial communities in sediments at cold methane seeps are important factors in controlling methane emission to the ocean and atmosphere. Here, we investigated the distribution and carbon isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) responsible for the anaerobic oxidation of methane (AOM) at different cold seep provinces of Hydrate Ridge, Cascadia margin. The special focus was on their relation to in situ cell abundances and methane turnover. In general, maxima in biomarker abundances and minima in carbon isotope signatures correlated with maxima in AOM and sulphate reduction as well as with consortium biomass. We found ANME-2a/DSS aggregates associated with high abundances of sn-2,3-di-O-isoprenoidal glycerol ethers (archaeol, sn-2-hydroxyarchaeol) and specific bacterial fatty acids (C16:1omega5c, cyC17:0omega5,6) as well as with high methane fluxes (Beggiatoa site). The low to medium flux site (Calyptogena field) was dominated by ANME-2c/DSS aggregates and contained less of both compound classes but more of AOM-related glycerol dialkyl glycerol tetraethers (GDGTs). ANME-1 archaea dominated deeper sediment horizons at the Calyptogena field where sn-1,2-di-O-alkyl glycerol ethers (DAGEs), archaeol, methyl-branched fatty acids (ai-C15:0, i-C16:0, ai-C17:0), and diagnostic GDGTs were prevailing. AOM-specific bacterial and archaeal biomarkers in these sediment strata generally revealed very similar d13C-values of around -100 per mill. In ANME-2-dominated sediment sections, archaeal biomarkers were even more 13C-depleted (down to -120 per mill), whereas bacterial biomarkers were found to be likewise 13C-depleted as in ANME-1-dominated sediment layers (d13C: -100 per mill). The zero flux site (Acharax field), containing only a few numbers of ANME-2/DSS aggregates, however, provided no specific biomarker pattern. Deeper sediment sections (below 20 cm sediment depth) from Beggiatoa covered areas which included solid layers of methane gas hydrates contained ANME-2/DSS typical biomarkers showing subsurface peaks combined with negative shifts in carbon isotopic compositions. The maxima were detected just above the hydrate layers, indicating that methane stored in the hydrates may be available for the microbial community. The observed variations in biomarker abundances and 13C-depletions are indicative of multiple environmental and physiological factors selecting for different AOM consortia (ANME-2a/DSS, ANME-2c/DSS, ANME-1) along horizontal and vertical gradients of cold seep settings.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Investigation of diagenesis in sediment core CRP-1 from the Ross Sea, Antarctica

A diagenetic study was carried out on the cored Miocene section in CRP-1 by thin-section, X-ray diffraction, scanning electron microscope, electron microprobe and stable isotopic analysis. Carbonate (calcite, siderite) microconcretions occur locally within intergranular pores and open fractures, and some sands are cemented by microcrystalline calcite. Calcite cement at 115.12 mbsf (metres below sea floor) and possibly microconcretionary calcite at 44.62 mbsf record infiltration of meteoric waters into the section, consistent with sequence stratigraphic evidence for multiple glacial advances over the CRP-1 drillsite. Diagenetic carbonates incorporated carbon derived from both organic matter and marine carbonate. Carbon isotope data are consistent with microconcretion formation at shallow depths. Sandstones are poorly compacted and, despite containing a large component of chemically unstable grains, are virtually unaltered. Preservation of the chemically unstable grain component reflects the cold climate depositional setting and shallow maximum burial depths.

Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

Assemblages and isotopic signals of modern ostracodes and host waters from Patagonia, Argentine

Ostracode species assemblages and stable oxygen and carbon isotope ratios of living and recent ostracodes, together with delta18O and delta13C_DIC values of host water samples, provide a first data set that characterizes a wide range of modern aquatic environments in the Laguna Cari-Laufquen (41°S, 68 - 69°W) and the Lago Cardiel area (48 - 49°S, 70 - 71°W) in Patagonia, Argentina. This data set will ultimately be used to interpret and calibrate data acquired from lake sediment cores with the goal of reconstructing past climate. Species assemblages and isotope values can be assigned to three groups; (1) springs, seeps and streams, (2) permanent ponds and lakes, and (3) ephemeral ponds and lakes. Springs, seeps and streams are characterized by Darwinula sp., Heterocypris incongruens, Eucypris fontana, Amphicypris nobilis and Ilyocypris ramirezi. Ostracode and water isotope values range between -13 and -5 per mil for oxygen, and between -15 and -3 per mil for carbon. They are the most negative of the entire sample set, reflecting ground water input with little or no evaporative enrichment. Limnocythere patagonica, Eucypris labyrinthica, Limnocythere sp. and Eucypris aff. fontana are typical species of permanent ponds and lakes. Isotope values indicate high degree of evaporation of lake waters relative to feeder springs and streams and range between -7 and +5 per mil for oxygen, and -5 and +4 per mil for carbon. Limnocythere rionegroensis is the dominant species in ephemeral ponds and lakes. These systems display the most enriched isotope values in both ostracodes and host waters, extending from -5 to +7 per mil for oxygen, and from -5 to +6 per mil for carbon. Living ostracodes show a positive offset from equilibrium values of up to 2 per mil for oxygen. Carbon-isotope values are up to 6? more negative than equilibrium values in highly productive pools. Comparison of ostracode and host water isotope signals permits assessment of the life span of the aquatic environments. Valves from dead ostracodes collected from ephemeral ponds and lakes show a wide scatter with each sample providing a snapshot of the seasonal history of the host water. The presence of the stream species Ilyocypris ramirezi and a wide range of ostracode isotope values suggest that ephemeral ponds and lakes are fed by streams during spring run-off and seasonally dry. A temporary character is also indicated by Heterocypris incongruens, a drought-resistant species that occupies most springs and seeps. In addition, Limnocythere rionegroensis has adjusted its reproduction strategies to its environment. Whereas only females were collected in fresh host waters, males were found in ephemeral ponds and lakes with higher solute content. Sexual reproduction seems to be the more successful reproduction strategy in high and variable salinities and seasonal droughts. The temporary character of the aquatic environments shows that the availability of meteoric water controls the life span of host waters and underlines the sensitivity of the area to changes in precipitation.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Tab. 1 Mole % CO2 and 13C values of CO2 at baseline and at the final monitoring event for the eight observation wells

During CO2 storage operations in mature oilfields or saline aquifers it is desirable to trace the movement of injected CO2 for verification and safety purposes. We demonstrate the successful use of carbon isotope abundance ratios for tracing the movement of CO2 injected at the Cardium CO2 Storage Monitoring project in Alberta between 2005 and 2007. Injected CO2 had a d13C value of -4.6±1.1 per mil that was more than 10 per mil higher than the carbon isotope ratios of casing gas CO2 prior to CO2 injection with average d13C values ranging from -15.9 to -23.5 per mil. After commencement of CO2 injection, d13C values of casing gas CO2 increased in all observation wells towards those of the injected CO2 consistent with a two-source end-member mixing model. At four wells located in a NE-SW trend with respect to the injection wells, breakthrough of injected CO2 was registered chemically (>50 mol % CO2) and isotopically 1-6 months after commencement of CO2 injection resulting in cumulative CO2 fluxes exceeding 100000 m**3 during the observation period. At four other wells, casing gas CO2 contents remained below 5 mol % resulting in low cumulative CO2 fluxes (<2000 m**3) throughout the entire observation period, but carbon isotope ratios indicated contributions between <30 and 80% of injected CO2. Therefore, we conclude that monitoring the movement of CO2 in the injection reservoir with geochemical and isotopic techniques is an effective approach to determine plume expansion and to identify potential preferential flow paths provided that the isotopic composition of injected CO2 is constant and distinct from that of baseline CO2.

Paleomegnetic and geochemistry of sediments from the early Aptian Oceanic Anoxic Event

The early Aptian Oceanic Anoxic Event (OAE1a, 120 Ma) represents a geologically brief time interval in the mid-Cretaceous greenhouse world that is characterized by increased organic carbon accumulation in marine sediments, sudden biotic changes, and abrupt carbon-isotope excursions indicative of significant perturbations to global carbon cycling. The brevity of these drastic environmental changes (< 10**6 year) and the typically 10**6 year temporal resolution of the available chronologies, however, represent a critical gap in our knowledge of OAE1a. We have conducted a high-resolution investigation of three widely distributed sections, including the Cismon APTICORE in Italy, Santa Rosa Canyon in northeastern Mexico, and Deep Sea Drilling Project (DSDP) Site 398 off the Iberian margin in the North Atlantic Ocean, which represent a range of depositional environments where condensed and moderately expanded OAE1a intervals are recorded. The objectives of this study are to establish orbital chronologies for these sections and to construct a common, high-resolution timescale for OAE1a. Spectral analyses of the closely-spaced (corresponding to ~5 to 10 kyr) measurements of calcium carbonate content of the APTICORE, magnetic susceptibility (MS) and anhysteretic remanent magnetization (ARM) of the Santa Rosa samples, and MS, ARM and ARM/IRM, where IRM is isothermal remanent magnetization, of Site 398 samples reveal statistically significant cycles. These cycles exhibit periodicity ratios and modulation patterns similar to those of the mid-Cretaceous orbital cycles, suggesting that orbital variations may have modulated depositional processes. Orbital control allows us to estimate the duration of unique, globally identifiable stages of OAE1a. Although OAE1a had a duration of ~1.0 to 1.3 Myr, the initial perturbation represented by the negative carbon-isotope excursion was rapid, lasting for ~27-44 kyr. This estimate could serve as a basis for constraining triggering mechanisms for OAE1a.

Age determination and grwoth rates of stalagmites and stalactites from the Okshola cave, Fauske, northern Norway

The sensitivity of terrestrial environments to past changes in heat transport is expected to be manifested in Holocene climate proxy records on millennial to seasonal timescales. Stalagmite formation in the Okshola cave near Fauske (northern Norway) began at about 10.4 ka, soon after the valley was deglaciated. Past monitoring of the cave and surface has revealed stable modern conditions with uniform drip rates, relative humidity and temperature. Stable isotope records from two stalagmites provide time-series spanning from c. 10380 yr to AD 1997; a banded, multi-coloured stalagmite (Oks82) was formed between 10380 yr and 5050 yr, whereas a pristine, white stalagmite (FM3) covers the period from ~7500 yr to the present. The stable oxygen isotope (delta18Oc), stable carbon isotope (delta13Cc), and growth rate records are interpreted as showing i) a negative correlation between cave/surface temperature and delta18Oc, ii) a positive correlation between wetness and delta13Cc, and iii) a positive correlation between temperature and growth rate. Following this, the data from Okshola show that the Holocene was characterised by high-variability climate in the early part, low-variability climate in the middle part, and high-variability climate and shifts between two distinct modes in the late part. A total of nine Scandinavian stalagmite delta18Oc records of comparable dating precision are now available for parts or most of the Holocene. None of them show a clear Holocene thermal optimum, suggesting that they are influenced by annual mean temperature (cave temperature) rather than seasonal temperature. For the last 1000 years, delta18Oc values display a depletion-enrichment-depletion pattern commonly interpreted as reflecting the conventional view on climate development for the last millennium. Although the delta18Oc records show similar patterns and amplitudes of change, the main challenges for utilising high-latitude stalagmites as palaeoclimate archives are i) the accuracy of the age models, ii) the ambiguity of the proxy signals, and iii) calibration with monitoring data.

Paleoproductivity reconstruction for the eastern equatorial Pacific

Productivity at six core locations in the eastern equatorial Pacific (EEP) was reconstructed with a benthic foraminiferal transfer function. The core records show strong regionality, especially where affected by Peru margin upwelling of deeper Equatorial Undercurrent Water (EUC) (originally coming from the subantarctic). This "Peru margin" record differs from that seen along the equator where divergence leads to shallow upwelling, and it is generally inverse to that seen in cores outside the areas of equatorial upwelling. Principal components analysis shows that the main productivity pattern correlates well to the global oxygen isotope record and has lowest values during isotope stages 2 and 4. In addition to this, equatorial cores show a higher frequency pattern of variation which becomes much more pronounced during MIS 3 and 2. The reconstructions based on benthic foraminifera were tested against those from nonaccumulation rate based inorganic chemical proxies of export production. These were found to correlate well in the region influenced by Peru upwelling, and also to share common features for sites along the equator. All the nonaccumulation rate based paleotracers are consistent with one another and differ from accumulation rate derived proxies. The differences between the two classes of paleotracers may result from uncertainties in calculating actual biogenic fluxes since 230Th-normalized results conform more to those we obtained. Analysis of planktonic carbon isotope values for the EEP, and their comparison to the record of the Pacific subantarctic, indicates that the subantarctic contribution to the EUC was reduced during MIS 3 and 2.

Geochemistry of Late Paleocene thermal maximum sediments

The late Paleocene thermal maximum (LPTM) was a dramatic, short-term global warming event that occurred ~55 Ma. Warming of high-latitude surface waters and global deep waters during the LPTM has been well documented; however, current data suggest that subtropical and tropical sea surface temperatures (SSTs) did not change during the event. Conventional paradigms of global climate change, such as CO2-induced greenhouse warming, predict greater warming in the high latitudes than in the tropics or subtropics but, nonetheless, cannot account for the stable tropical/subtropical SSTs. We measured the stable isotope values of well-preserved late Paleocene to early Eocene planktonic foraminifera from South Atlantic Deep Sea Drilling Project (DSDP) Site 527 to evaluate the subtropical response to the climatic and environmental changes of the LPTM. Planktonic foraminiferal d18O values at Site 527 decrease by ~0.94 per mil from pre-LPTM to excursion values, providing the first evidence for subtropical warming during the LPTM. We estimate that subtropical South Atlantic SSTs warmed by at least ~1°-4°C, on the basis of possible changes in evaporation and precipitation. The new evidence for subtropical SST warming supports a greenhouse mechanism for global warming involving elevated atmospheric CO2 levels.

Age determination of sediment cores close to the Strait of Gibralta

A suit of sediment cores close to and south of the Strait of Gibraltar (12°-36°N, 500-2800 m water depth) were analyzed for stable isotopes in epibenthic foraminifers Cibicidoides wuellerstorfi and Planulina ariminensis. During peak glacial times, the data exhibit higher delta13C values of up to 1.6 per mil at intermediate depths near the Strait of Gibraltar (36°N). The values decrease to the south as evidenced by our data, but also to the north as revealed by data of intermediate depth cores north of 38°N (in Duplessy et al. (1987)). Thus, the distribution pattern of delta13C provides crucial evidence for an increased influence of nutrient depleted Mediterranean Outflow Water (MOW) on the glacial northeast Atlantic hydrography. During oxygen isotope Terminations I and II, the meridional carbon isotope gradient indicates a significantly decreased but still active MOW. As deduced from the delta18O fluctuations, the temperatures of the MOW in the Atlantic were lower during glacial times by as much as 5°C. During glacial times and during Termination I the maximum delta13C values of the MOW correlate with minimum values of the North Atlantic Deep Water (NADW) and vice versa. This inverse response to climatic change of the carbon isotope signals of both water masses indicates, that the supply of saline MOW to the north Atlantic may be less important for the formation of NADW than previously assumed.

Phosphorus concentrations and accumulation rates of ODP Leg 130 sites

Little is known about the fluxes to and from the ocean during the Cenozoic of phosphorus (P), a limiting nutrient for oceanic primary productivity and organic carbon burial on geologic timescales. Previous studies have concluded that dissolved river fluxes increased worldwide during the Cenozoic and that organic carbon burial decreased relative to calcium carbonate burial and perhaps in absolute terms as well. To examine the apparent contradiction between increased river fluxes of P (assuming P fluxes behave like the others) expected to drive increased organic carbon burial and observations indicating decreased organic carbon burial, we determined P accumulation rates for equatorial Pacific sediments from Ocean Drilling Program leg 138 sites in the eastern equatorial Pacific and leg 130 sites on the Ontong Java Plateau in the western equatorial Pacific. Although there are site specific and depth dependent effects on P accumulation rates, there are important features common to the records at all sites. P accumulation rates declined from 50 to 20 Ma, showed some variability from 20 to 10 Ma, and had a substantial peak from 9 to 3 Ma centered at 5-6 Ma. These changes in P accumulation rates for the equatorial Pacific are equivalent to substantial changes in the P mass balance. However, the pattern resembles neither that of weathering flux indicators (87Sr/86Sr and Ge/Si ratios) nor that of the carbon isotope record reflecting changes in organic carbon burial rates. Although these P accumulation rate patterns need confirmation from other regions with sediment burial significant in global mass balances (e.g., the North Pacific and Southern Ocean), it appears that P weathering inputs to the ocean are decoupled from those of other elements and that further exploration is needed of the relationship between P burial and net organic carbon burial.