ALBERT

Description: Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Description: Assessment of changes in surface ocean conditions, in particular, sea-surface temperature (SST), is essential to understand long-term changes in climate especially in regions where continental climate is strongly influenced by oceanographic processes. To evaluate changes in SST in the northeast Pacific, we have analyzed long-chain alkenones of prymnesiophyte origin at 38 depths in a piston and associated trigger core collected beneath the contemporary core of the California Current System at 42°N, ~270 km off the coast of Oregon/California. The samples span 30,000 years of deposition at this location. Unsaturation patterns (UK'37) in the alkenone series display a statistically significant difference (p 〈〈0.001) between interglacial (0.44 ± 0.02, n = 11) and glacial (0.29 ± 0.04, n = 20) intervals of the cores. Detailed examination of other compositional features of the C37, C38, C39 alkenone series and a related C36 alkenoate series measured downcore suggests the published UK'37 - temperature calibration (UK'37 = 0.034 * T + 0.039 ) , defined for cultures of a strain of Emiliania huxleyi isolated from the subarctic Pacific, provides best estimates of winter SST at our study site. This inference is purely statistical and does not imply, however, that the phytoplankton source of these biomarkers is most productive in winter or at the ocean surface. The temperature record for UK'37 implies (1) an ~4°C shift occurred in winter SST from ~7.5 ± 1.1°C at the last glacial maximum to ~11.7 ± 0.7°C in the present interglacial period, and (2) this warming trend was confined to the time frame 14-10 Ka within the glacial to interglacial transition period. These conclusions are corroborated entirely by results from an independent SST transformation of radiolarian species assemblage data obtained from the same core materials.

Description: 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.

Description: Eleven sediment samples taken downcore and representing the past 26 kyr of deposition at MANOP site C (0°57.2°N, 138°57.3°W) were analyzed for lipid biomarker composition. Biomarkers of both terrestrial and marine sources of organic carbon were identified. In general, concentration profiles for these biomarkers and for total organic carbon (TOC) displayed three common stratigraphic features in the time series: (1) a maximum within the surface sediment mixed layer (〈=4 ka); (2) a broad minimum extending throughout the interglacial deposit; and (3) a deep, pronounced maximum within the glacial deposit. Using the biomarker records, a simple binary mixing model is described that assesses the proportion of terrestrial to marine TOC in these sediments. Best estimates from this model suggest that ~20% of the TOC is land-derived, introduced by long-range eolian transport, and the remainder is derived from marine productivity. The direct correlation between the records for terrestrial and marine TOC with depth in this core fits an interpretation that primary productivity at site C has been controlled by wind-driven upwelling at least over the last glacial/interglacial cycle. The biomarker records place the greatest wind strength and highest primary productivity within the time frame of 18 to 22 kyr B.P. Diagenetic effects limit our ability to ascertain directly from the biomarker records the absolute magnitude that different types of primary productivity have changed at this ocean location over the past 26 kyr.

Description: Iron is considered to play a large role in the cycling of Si in Fe-limited regions of the ocean, but little is known about its role in Si biogeochemistry outside these areas. Here, we present published sediment trap data, new nutrient profiles and high resolution sedimentary records (Si isotopes, Biogenic silica%, N% and C%) from the Gulf of California, a non-Fe-limited region, to investigate the history of Si cycling in this highly productive basin. Modern nutrient profiles show that silicic acid in subsurface waters is in excess relative to nitrate and is therefore incompletely utilized during moderate winter upwelling events. Modern data, however, suggest that during intense upwelling episodes, silicic acid is preferentially utilized relative to nitrate by the biota, which we suggest reflects transient iron limitation. Our new d30Si record from the Guaymas Basin shows dramatic variations at millennial timescales. Low δ30Si values synchronous with Heinrich events are interpreted as resulting from the decline in Si(OH)4 utilization at times of decreased upwelling strength, while nearly complete Si(OH)4 utilization was observed at times of invigorated upwelling and increased opal burial during the Holocene, the Bølling-Allerød and the last glacial period. We attribute the complete utilization of Si(OH)4 to the occurrence of transient Fe limitation at these times. Our study highlights the importance of Fe limitation on Si and C cycling in coastal upwelling regions and suggests that upwelling dynamics, in combination with Fe availability, have the potential to modulate marine Si distribution and opal burial even at short timescales.