Stable carbon isotope ratios of alkane of IODP Hole 302-M0004A

The Palaeocene/Eocene thermal maximum represents a period of rapid, extreme global warming approx ~55 million years ago, superimposed on an already warm world (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2). This warming is associated with a severe shoaling of the ocean calcite compensation depth **4 and a >2.5 per mil negative carbon isotope excursion in marine and soil carbonates (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2; Zachos et al., doi:10.1126/science.1109004). Together these observations indicate a massive release of 13C-depleted carbon (Zachos et al., doi:10.1126/science.1109004) and greenhouse-gas-induced warming. Recently, sediments were recovered from the central Arctic Ocean (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006), providing the first opportunity to evaluate the environmental response at the North Pole at this time. Here we present stable hydrogen and carbon isotope measurements of terrestrial-plant- and aquatic-derived n-alkanes that record changes in hydrology, including surface water salinity and precipitation, and the global carbon cycle. Hydrogen isotope records are interpreted as documenting decreased rainout during moisture transport from lower latitudes and increased moisture delivery to the Arctic at the onset of the Palaeocene/Eocene thermal maximum, consistent with predictions of poleward storm track migrations during global warming (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006). The terrestrial-plant carbon isotope excursion (about ~4.5 to ~6 per mil) is substantially larger than those of marine carbonates. Previously, this offset was explained by the physiological response of plants to increases in surface humidity (Bowen et al., 2004, doi:10.1038/nature03115). But this mechanism is not an effective explanation in this wet Arctic setting, leading us to hypothesize that the true magnitude of the excursion - and associated carbon input - was greater than originally surmised. Greater carbon release and strong hydrological cycle feedbacks may help explain the maintenance of this unprecedented warmth.of this unprecedented warmth.

(Table 3) Noble gas composition of dissociated gas hydrate specimens from ODP Leg 164 sites

Fractionation of the noble gases should occur during formation of a Structure I gas hydrate from water and CH4 such that CH4 hydrate is greatly enriched in Xenon. Noble gas concentrations and fractionation factors (F[4He], F[22Ne], F[86Kr], and F[132Xe] as well as R/Ra) were determined for eight gas hydrate specimens collected on Leg 164 to evaluate this theoretical possibility and to assess whether sufficient quantities of Xe are hosted in oceanic CH4 hydrate to account for Xe "missing" from the atmosphere. The simplest explanation for our results is that samples contain mixtures of air and two end-member gases. One of the end-member gases is depleted in Ne, but significantly enriched in Kr and Xe, as anticipated if the source of this gas involves fractionation during Structure I gas hydrate formation. However, although oceanic CH4 hydrate may be greatly enriched in Xe, simple mass balance calculations indicate that oceanic CH4 hydrate probably represents only a minor reservoir of terrestrial Xe. Noble gas analyses may play an important role in understanding the dynamics of gas hydrate reservoirs, but significantly more work is needed than presented here.

Relative abundance of pennate diatoms Thalassionema spp. and Thalassiothrix spp. im Upper Miocene-Lower Pliocene bulk sediment at ODP Hole 145-886B, North Pacific (Table 1)

Rapidly deposited Thalassionema-Thalassiothrti pennate diatom oozes previously have been described in Upper Miocene-Lower Pliocene sediment beneath the frontal boundary of the eastern equatorial Pacific. Here we document a new occurrence of Thalassionema-Thalassiothrix ooze in Upper Miocene-Lower Pliocene sediment beneath the frontal boundary of the subarctic North Pacific. The ooze is a 6 m interval of siliceous sediment at Ocean Drilling Program (ODP) sites 885/886 that was rapidly deposited between approximately 5.0 and 5.9 Ma. Bulk sediment in this interval may contain greater than 85% pennate diatom tests. There are also abundant laminae and pockets that are composed entirely of Thalassionema and Thalassiothrix diatoms. The presence of a rapidly deposited ooze dominated by pennate diatoms indicates unusual past conditions in the overlying surface waters. Time coincident deposition of such oozes at two distinct frontal boundary locations of the Pacific suggests that the unusual surface water conditions were causally linked to large-scale oceanographic change. This same oceanographic change most likely involved (1) addition of nutrients to the ocean, or (2) redistribution of nutrients within the ocean. The occurrence and origin of pennate diatom oozes may be a key component to an integrative understanding of late Neogene paleoceanography and biogeochemical cycling.

Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.

Correlation between wet bulk density and carbonate content from IODP Hole 321-U1338A, 321-U1338B and 321-U1338C

Sediment cores collected from the Eastern Equatorial Pacific Ocean display a clear positive second-order relationship between wet bulk density (WBD) and carbonate content. This has long interested the paleoceanography community because detailed Gamma Ray Attenuation Porosity Evaluator (GRAPE) measurements, which approximate WBD, might be used to determine records of carbonate content at very high temporal resolution. Although general causes for the relationship are known, they have not been presented and discussed systematically on the basis of first principles. In this study, we measure the mass and carbonate content of 50 sediment samples with known WBD from Site U1338, before and after rinsing with de-ionized water; we also determine the mass related proportion of coarse (> 63 µm) material. Samples exhibit clear relationships between WBD, carbonate content, mass loss upon rinsing, and grain size. We develop a series of mathematical expressions to describe these relationships, and solve them numerically. As noted by previous workers, the second-order relationship between WBD and carbonate content results from the mixing of biogenic carbonate and biogenic silica, which have different grain densities and different porosities. However, at high carbonate content, a wide range in WBD occurs because samples with greater amounts of coarse carbonate have higher porosity. Moreover compaction impacts carbonate particles more than biogenic silica particles. As such, a single two-component equation cannot be used to determine carbonate content accurately across depth intervals where both the porosity and type of carbonate vary. Instead, the WBD-carbonate relationship is described by an infinite series of curves, each which represents mixing of multiple sediment components with different densities and porosities. Dissolved ions also precipitate from pore space during sample drying, which adds mass to the sediment. Without rinsing samples, simple empirical relationships between WBD and carbonate content are further skewed by salt dilution.

Age and d18O analysis relating to Cenozoic greenhouse climatesXXX

Past episodes of greenhouse warming provide insight into the coupling of climate and the carbon cycle and thus may help to predict the consequences of unabated carbon emissions in the future.

Gas, water and volume characteristics during controlled degassing experiments on ODP Leg 164 PCS cores

A pressurized core with CH4 hydrate or dissolved CH4 should evolve gas volumes in a predictable manner as pressure is released over time at isothermal conditions. Incremental gas volumes were collected as pressure was released over time from 29 pressure core sampler (PCS) cores from Sites 994, 995, 996, and 997 on the Blake Ridge. Most of these cores were kept at or near 0ºC with an ice bath, and many of these cores yielded substantial quantities of CH4. Volume-pressure plots were constructed for 20 of these cores. Only five plots conform to expected volume and pressure changes for sediment cores with CH4 hydrate under initial pressure and temperature conditions. However, other evidence suggests that sediment in these five and at least five other PCS cores contained CH4 hydrate before core recovery and gas release. Detection of CH4 hydrate in a pressurized sediment core through volume-pressure relationships is complicated by two factors. First, significant quantities of CH4-poor borehole water fill the PCS and come into contact with the core. This leads to dilution of CH4 concentration in interstitial water and, in many cases, decomposition of CH4 hydrate before a degassing experiment begins. Second, degassing experiments were conducted after the PCS had equilibrated in an ice-water bath (0ºC). This temperature is significantly lower than in situ values in the sediment formation before core recovery. Our results and interpretations for PCS cores collected on Leg 164 imply that pressurized containers formerly used by the Deep Sea Drilling Project (DSDP) and currently used by ODP are not appropriately designed for direct detection of gas hydrate in sediment at in situ conditions through volume-pressure relationships.