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.

Geochemistry and foraminiferal stable isotoe record of sediment core SCS90-36

Changes in the Southeast Asia monsoon winds and surface circulation patterns since the last glaciation are inferred using multiple paleoceanographic indicators including planktic foraminifer faunal abundances, fauna and alkenones sea-surface temperature (SST) estimates, oxygen and carbon isotopes of planktic and benthic foraminifers, and sedimentary fluxes of carbonates and organic carbon obtained from deep-sea core SCS90-36 from the South China Sea (SCS) (17°59.70'N, 111°29.64'E at water depth 2050 m). All these paleoceanographic evidences indicate marked changes in the SCS ocean system over the last glacial toward the Holocene. Planktic foraminiferal faunal SST estimates show stable warm-season SST of 28.6°C, close to the modern value, throughout the glacial-interglacial cycle. In contrast, cold-season SST increases gradually from 23.6°C in the last glacial to a mean value of 26.4°C in the Holocene with a fluctuation of about 3°C during 13-16 ka. SST estimates by UK'37 method reveal less variability and are in average 1-3°C lower than the fauna-derived winter-season SST. These patterns reveal that the seasonality of the SST is not only higher by about 3-4°C in the glacial, but also a function of the winter season SST. Sedimentation rates decrease from the last glacial-deglacial stage to the Holocene due to a reduction in supply of terrigenous components, which led to an increase of carbonate contents. Total organic carbon (TOC) contents of primarily marine sources decrease from the last glacial-deglacial to the Holocene. The last deglaciation is also characterized by high surface productivity as indicated by increased ketones abundances and high mass accumulation rates (MAR) of the TOC and carbonates. The gradient of planktic foraminifer ocygen and carbon isotopes of between surface dwellers and deep dwellers increases significantly toward Termination I and Holocene, and is indiscernibly small in the carbon isotope gradient of between 14 and 24 ka, revealing a deep-mixing condition in surface layers prior to 10 ka. The glacial-interglacial fluctuation of the carbon isotope value of a benthic foraminifer is 0.61%. which is significantly larger than a global mean value. The large carbon isotope fluctuation indicates an amplification of marginal-sea effects which is most likely resulted from an increase in surface productivity in the northern SCS during the last glacial-deglacial stage. The multiple proxies consistently indicate that the last glacial-deglacial stage winter monsoon in the Southeast Asia was probably strengthened in the northern SCS, leading to a development of deep-mixing surface layer conditions and a more efficient nutrient cycling which supports more marine organic carbon production.

Alkenone UK37 measured in the upper water column at pump stations CariacoTrench, Peru and Vertex

A series of long-chain (C37, C38, C39), primarily di and tri-unsaturated methyl and ethyl ketones, first identified in sediments from Walvis Ridge off West Africa and from Black Sea (de Leeuw et al., 1979), has been found in marine sediments throughout the world (Brassell et al., 1986 doi:10.1038/320129a0). The marine coccolithophorid Emiliania huxleyi and members of the class Prymnesiophyceae are now the recognized sources of these compounds (Volkman et al., 1979; Marlowe, et al., 1984). Experiments with laboratory cultures of algae showed the degree of unsaturation in the ketone seris biosynthesized depends on growth temperature (Brassell et al., 1986; Marlowe, 1984), a physiological respons observed for classical membrane lipids (vanDeenen et al., 1972). Brassell and co-workers (Brassell et al., 198; Brassell et al., 1986b) thus proposed that systematic fluctuations in the unsaturation of these alkenones noted down-core in sediments from the Kane Gap region of the north-east tropical Atlantic Ocean and correlated with glacial-interglacial cycles provide an organic geochemical measure of past sea-surface water temperatures. Using laboratory cultures of E. huxleyi, we have calibrated changes in the unsaturation pattern of the long-chain ketone series versus growth temperature. The calibration curve is linear and accurtely predicts unsuturation patterns observed in natural particulate materials collected from oceanic waters of known temperature. We present evidence supporting the proposed paleotemperature hypothesis (Brassell et al., 1986, Brassel et al., 1986b) and suggesting absolute 'sea-surface temperatures' for a given oceanic location can be estimated from an analysis of long-chain ketone compositions preserved in glacial and interglacial horizons of deep-sea sediment cores.

Glycerol dialkyl glycerol tetraethers (GDGT) abundance in suspended particulate matter from the South-west and Equatorial Atlantic Ocean

The TEX86 paleotemperature proxy is based on archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids preserved in marine sediments, yet both the influence of different physiological factors on the structural distribution of GDGTs, and the mechanism(s) by which GDGTs are exported to marine sediments remain unclear. In particular, TEX86 temperatures derived directly from suspended particulate matter (SPM) in the water column can diverge strongly from corresponding in situ temperatures. Here we investigated the abundance and structural distribution of GDGTs in the South-west and Equatorial Atlantic Ocean by examining SPM collected from four surface 1000 m depth profiles spanning 48 degrees of latitude. The depth distribution of GDGTs was consistent with our current understanding of marine archaeal ecology, and specifically of ammonia-oxidizing Thaumarchaeota. Maximum GDGT concentrations occurred at the base of the primary NO2- maximum. Core GDGTs dominated the structural distribution in surface waters, while intact polar GDGTs - thought to potentially indicate live cells - were more abundant at all depths below the maximum NO2- concentration. When integrated through the upper 1000 m of the water column, > 98% of GDGTs were present in waters at and below the depth of the primary NO2- maximum. TEX86-calculated temperatures showed local minima at the depth of the NO2- maximum, while the ratio of GDGT 2:GDGT 3 [2/3] increased with depth throughout the upper water column. These results were used to model the depth of origin for GDGTs exported to sediments. By comparing our SPM data to published TEX86 values and [2/3] ratios from sediments near our study sites, we conclude that most GDGTs are exported from the depth of maximum GDGT concentrations, near the subsurface NO2- maximum (~80-250 m). This indicates that local ammonia oxidation dynamics are important regional controls on the GDGT ratios preserved in sediments. Predicting the extent to which subsurface variations in archaeal activity may influence the sedimentary TEX86 record will require a better understanding of how site-specific productivity and particle dynamics in the upper water column influence the depth of origin for exported organic matter.