Contents and stable carbon isotope compositions of biomarkers indicative for AOM-communities dominated by different ANME groups in two carbonate samples from Hydrate Hole pockmark

Different types of seep carbonates were recovered from the 'Kouilou pockmarks' on the Congo deep-sea fan in approximately 3100 m water depth. The carbonate aggregates are represented by pyritiferous nodules, crusts and slabs, tubes, and filled molds. The latter are interpreted to represent casts of former burrows of bivalves and holothurians. The nodules consisting of high-Mg-calcite apparently formed deeper within the sediments than the predominantly aragonitic crusts and slabs. Nodule formation was caused by anaerobic oxidation of methane dominantly involving archaea of the phylogenetic ANME-1 group, whereas aragonitic crusts resulted from the activity of archaea of the ANME-2 cluster. Evidence for this correlation is based on the distribution of specific biomarkers in the two types of carbonate aggregates, showing higher hydroxyarchaeol to archaeol ratios in the crusts as opposed to nodules. Formation of crusts closer to the seafloor than nodules is indicated by higher carbonate contents of crusts, probably reflecting higher porosities of the host sediment during carbonate formation. This finding is supported by lower d18O values of crusts, agreeing with precipitation from pore waters similar in composition to seawater. The aragonitic mineralogy of the crusts is also in accord with precipitation from sulfate-rich pore waters similar to seawater. Moreover, the interpretation regarding the relative depth of formation of crusts and nodules agrees with the commonly observed pattern that ANME-1 archaea tend to occur deeper in the sediment than members of the ANME-2 group. Methane represents the predominant carbon source of all carbonates (d13C values as low as -58.9 per mil V-PDB) and the encrusted archaeal biomarkers (d13C values as low as -140 per mil V-PDB). Oxygen isotope values of some nodular carbonates, ranging from + 3.9 to + 5.1per mil V-PDB, are too high for precipitation in equilibrium with seawater, probably reflecting the destabilization of gas hydrates, which are particularly abundant at the Kouilou pockmarks.

Stable carbon isotope record of planktonic foraminifera and organic matter from sediment cores in the Gulf of Aqaba

The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in delta13CDIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The delta13C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63? over the last two centuries. This decrease seems to track the decrease of delta13CDIC in surface waters, which is mainly caused by the increase of anthropogenic input of 13C-depleted CO2 into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (delta13Corg) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal delta13C. Furthermore, direct measurements of seawater show that delta13C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 per mil during the period 1979-2000. The average annual decrease is 0.021 per mil, which is similar to that observed globally. The delta13C values of planktonic foraminifera combined with organic matter delta13C from marine sediments are good indicators for reconstructing past changes in atmospheric CO2 concentrations from the northern Gulf of Aqaba.

Seawater carbonate chemistry, stable carbon isotope fractionation and growth rate during experiments with marine phytoplankton community, 1999

Stable carbon isotope fractionation (%) of 7 marine phytoplankton species grown in different irradiance cycles was measured under nutrient-replete conditions at a high light intensity in batch cultures. Compared to experiments under continuous light, all species exhibited a significantly higher instantaneous growth rate (pi), defined as the rate of carbon fixation during the photo period, when cultivated at 12:12 h. 16:8 h, or 186 h light:dark (L/D) cycles. Isotopic fractionation by the diatoms Skeletonema costatum, Asterionella glacialis, Thalassiosira punctigera, and Coscinodiscus wailesii (Group I) was 4 to 6% lower in a 16:8 h L/D cycle than under continuous light, which we attribute to differences in pi. In contrast, E, in Phaeodactylum tn'cornutum, Thalassiosira weissflogii, and in the dinoflagellate Scrippsiella trochoidea (Group 11) was largely insensitive to day length-related differences in instantaneous growth rate. Since other studies have reported growth-rate dependent fractionation under N-limited conditions in P. tricornutum, pi-related effects on fractionation apparently depend on the factor controlling growth rate. We suggest that a general relationship between E, and pi/[C02,,,] may not exist. For 1 species of each group we tested the effect of variable CO2 concentration, [COz,,,], on isotopic fractionation. A decrease in [CO2,,,] from ca 26 to 3 pm01 kg-' caused a decrease in E, by less than 3%0 This indicates that variation in h in response to changes in day length has a similar or even greater effect on isotopic fractionation than [COz,,,] m some of the species tested. In both groups E, tended to be higher in smaller species at comparable growth rates. In 24 and 48 h time series the algal cells became progressively enriched in 13C during the day and the first hours of the dark period, followed by l3C depletion in the 2 h before beginning of the following Light period. The daily amplitude of the algal isotopic composition (613C), however, was <1.5%0, which demonstrates that diurnal variation in Fl3C is relatively small.

Stable carbon isotope compositions and concentrations of biphytanes from IODP Hole 311-U1327C and 311-U1328B

We have investigated the distributions and carbon isotopic compositions of archaeal membrane lipids in gas-hydrate-bearing sediments collected from the northern Cascadia Margin offshore from Vancouver Island (Sites U1327 and U1328) by the R/V JOIDES Resolution during IODP Expedition 311. Archaeal lipid biomarkers, including glycerol dialkyl glycerol tetraethers (GDGTs), tend to become abundant below 100 mbsf (meters below sea floor). Tricyclic biphytane (BP[3]; which is a robust biomarker derived from GDGT), crenarchaeol, and other BPs exhibit d13C values of ca. -20 per mil, and become abundant between 130 and 230 mbsf at Site U1328. In this depth range, concentrations of ammonium and phosphate in interstitial waters also increase, suggesting that a larger population and higher activity of heterotrophic community consisting of crenarchaeota and other archaea decompose the sedimentary organic matter, thereby liberating ammonium and phosphate. Such crenarchaeotic activity can produce other metabolic products such as molecular hydrogen by fermentation of organic matter during diagenesis. Furthermore, near the organic matter decomposition zone (130 to 230 mbsf), a probable methanogen biomarker (13C-depleted BP[1] with d13C values as low as -48.8 per mil) becomes abundant, indicating that methanogens utilize these diagenetic products. The molecular and isotopic distributions of archaeal lipid biomarkers indicate that the archaeal community plays an important role in the biogeochemical cycles of deep-sea sediments, including both methanogenesis and nutrient recycling.

Bulk stable carbon and oxygen isotopes from ODP Site 1258, and Fe intensities from ODP Site 1262, and minimal tuning age model options for ODP Site 1258 and 1262

Timing is crucial to understanding the causes and consequences of events in Earth history. The calibration of geological time relies heavily on the accuracy of radioisotopic and astronomical dating. Uncertainties in the computations of Earth's orbital parameters and in radioisotopic dating have hampered the construction of a reliable astronomically calibrated time scale beyond 40 Ma. Attempts to construct a robust astronomically tuned time scale for the early Paleogene by integrating radioisotopic and astronomical dating are only partially consistent. Here, using the new La2010 and La2011 orbital solutions, we present the first accurate astronomically calibrated time scale for the early Paleogene (47-65 Ma) uniquely based on astronomical tuning and thus independent of the radioisotopic determination of the Fish Canyon standard. Comparison with geological data confirms the stability of the new La2011 solution back to ~54 Ma. Subsequent anchoring of floating chronologies to the La2011 solution using the very long eccentricity nodes provides an absolute age of 55.530 {plus minus} 0.05 Ma for the onset of the Paleocene/Eocene Thermal Maximum (PETM), 54.850 {plus minus} 0.05 Ma for the early Eocene ash -17, and 65.250 {plus minus} 0.06 Ma for the K/Pg boundary. The new astrochronology presented here indicates that the intercalibration and synchronization of U/Pb and 40Ar/39Ar radiometric geochronology is much more challenging than previously thought.

Stable carbon and oxygen isotope record of planktonic foraminifera across the Paleocene-Eocene boundary

The early Cenozoic marine carbon isotopic record is marked by a long-term shift from high d13C values in the late Paleocene to values that are 2 to 3 lower in the early Eocene. The shift is recorded in fossil carbonates from each ocean basin and represents a large change in the distribution of 12C between the ocean and other carbon reservoirs. Superimposed upon this long-term shift are several distinct carbon isotopic negative excursions that are also recorded globally. These carbon isotopic 'events' near the Paleocene-Eocene boundary provide strati-graphic information that can facilitate intersite correlations between marine and non-marine sequences. Here we present a detailed marine carbon isotopic stratigraphy across the Paleocene-Eocene boundary that is constrained by calcareous nannofossil and planktonic foraminifera bio-stratigraphy and magnetostratigraphy. We show that several distinct carbon isotopic changes are recorded in uppermost Paleocene and lowermost Eocene marine biogenic carbonate sediments. At least one of these isotopic changes in the ocean's carbon isotopic composition was transmitted to terrestrial carbon reservoirs, including plant biomass via atmospheric CO2. As a consequence of this exchange of 12C between the ocean and terrestrial carbon reservoirs, it is possible to use carbon isotope stratigraphy to correlate the uppermost Paleocene and lowermost Eocene non-fossiliferous terrestrial sediments of the Paris Basin with marine sequences.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Stable carbon and oxygen isotope record od IODP Hole 306-U1313

The Mid-Pleistocene transition (MPT) was the time when quasi-periodic (? 100 kyr), high-amplitude glacial variability developed in the absence of any significant change in the character of orbital forcing, leading to the establishment of the characteristic pattern of late Pleistocene climate variability. It has long been known that the interval around 900 ka stands out as a critical point of the MPT, when major glaciations started occurring most notably in the northern hemisphere. Here we examine the record of climatic conditions during this significant interval, using high-resolution stable isotope records from benthic and planktonic foraminifera from a sediment core in the North Atlantic (Integrated Ocean Drilling Program Expedition 306, Site U1313). We have considered the time interval from late in Marine Isotope Stage (MIS) 23 to MIS 20 (910 to 790 ka). Our data indicate that interglacial MIS 21 was a climatically unstable period and was broken into four interstadial periods, which have been identified and correlated across the North Atlantic region. These extra peaks tend to contradict previous studies that interpreted the MIS 21 variability as consisting essentially of a linear response to cyclical changes in orbital parameters. Cooling events in the surface record during MIS 21 were associated with low benthic carbon isotope excursions, suggesting a coupling between surface temperature changes and the strength of the Atlantic meridional overturning circulation. Time series analysis performed on the whole interval indicates that benthic and planktonic oxygen isotopes have significant concentrations of spectral power centered on periods of 10.7 kyr and 6 kyr, which is in agreement with the second and forth harmonic of precession. The excellent correspondence between the foraminifera d18O records and insolation variations at the Equator in March and September suggests that a mechanism related to low-latitude precession variations, advected to the high latitudes by tropical convective processes, might have generated such a response. This scenario accounts for the presence of oscillations at frequencies equal to precession harmonics at Site U1313, as well as the occurrence of higher amplitude oscillations between the MIS22/21 transition and most of MIS 21, times of enhanced insolation variability.

Stable carbon and oxygen isotope record of IODP Site 306-U1313, MIS 23-19

Since the seminal work by Hays et al. (1976), a plethora of studies has demonstrated a correlation between orbital variations and climatic change. However, information on how changes in orbital boundary conditions affected the frequency and amplitude of millennial-scale climate variability is still fragmentary. The Marine Isotope Stage (MIS) 19, an interglacial centred at around 785 ka, provides an opportunity to pursue this question and test the hypothesis that the long-term processes set up the boundary conditions within which the short-term processes operate. Similarly to the current interglacial, MIS 19 is characterised by a minimum of the 400-kyr eccentricity cycle, subdued amplitude of precessional changes, and small amplitude variations in insolation. Here we examine the record of climatic conditions during MIS 19 using high-resolution stable isotope records from benthic and planktonic foraminifera from a sedimentary sequence in the North Atlantic (Integrated Ocean Drilling Program Expedition 306, Site U1313) in order to assess the stability and duration of this interglacial, and evaluate the climate system's response in the millennial band to known orbitally induced insolation changes. Benthic and planktonic foraminiferal d18O values indicate relatively stable conditions during the peak warmth of MIS 19, but sea-surface and deep-water reconstructions start diverging during the transition towards the glacial MIS 18, when large, cold excursions disrupt the surface waters whereas low amplitude millennial scale fluctuations persist in the deep waters as recorded by the oxygen isotope signal. The glacial inception occurred at ~779 ka, in agreement with an increased abundance of tetra-unsaturated alkenones, reflecting the influence of icebergs and associated meltwater pulses and high-latitude waters at the study site. After having combined the new results with previous data from the same site, and using a variety of time series analysis techniques, we evaluate the evolution of millennial climate variability in response to changing orbital boundary conditions during the Early-Middle Pleistocene. Suborbital variability in both surface- and deep-water records is mainly concentrated at a period of ~11 kyr and, additionally, at ~5.8 and ~3.9 kyr in the deep ocean; these periods are equal to harmonics of precession band oscillations. The fact that the response at the 11 kyr period increased over the same interval during which the amplitude of the response to the precessional cycle increased supports the notion that most of the variance in the 11 kyr band in the sedimentary record is nonlinearly transferred from precession band oscillations. Considering that these periodicities are important features in the equatorial and intertropical insolation, these observations are in line with the view that the low-latitude regions play an important role in the response of the climate system to the astronomical forcing. We conclude that the effect of the orbitally induced insolation is of fundamental importance in regulating the timing and amplitude of millennial scale climate variability.