Contents of organic compounds in sediments from DSDP Legs 1 and 4

Fifteen sediment samples were studied from five drill sites recovered by the Glomar Challenger on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids. Carbon isotope (dC13) data [values <(-26)?, relative to PDB], long-chain n-alkyl hydrocarbons (>>C27) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized. The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.

(Table 1) Carbon and isotopic composition of organic carbon in sediments from DSDP Leg 56 Holes

We have analyzed inorganic and organic carbons and determined the isotopic composition of both sedimentary organic carbon and inorganic carbon in carbonates contained in sediments recovered from Holes 434, 434A, 434B, 435, and 435A in the landward slope of Japan and from Hole 436 in the oceanic slope of the Japan Trench. Both inorganic and organic carbons were assayed at the P. P. Shirshov Institute of Oceanology, in the same sample, using the Knopp technique and measuring evolved CO2 gravimetrically. Each sample was analyzed twice in parallel. Measurements were of a ±0.05 per cent accuracy and a probability level of 0.95. Carbon isotopic analysis was carried out on a MI-1305 mass spectrometer at the I. M. Gubkin Institute of Petrochemical and Gas Industry and the results presented as dC13 values related to the PDB standard. The procedure for preparing samples for organic carbon isotopic analysis involved (1) drying damp sediments at 60°C; (2) treating samples, while heating, with 10 N HCl to remove carbonate carbon; and (3) evaporating surplus HCl at 60°C. The organic substance was turned to CO2 by oxidizing it in an oxygen atmosphere. To prepare samples for inorganic carbon isotopic analysis we decomposed the carbonates with orthophosphoric acid and refined the gas evolved. The dC13 measurements, including a full cycle of sample preparation, were of a ±0.5 per cent accuracy and a probability level of 0.95.

Modeling the sensitivity of precipitation oxygen isotopes to the Last Glacial Maximum boundary conditions: A study using Community Atmosphere Model (CAM3.0)

To understand the validity of d18O proxy records as indicators of past temperature change, a series of experiments was conducted using an atmospheric general circulation model fitted with water isotope tracers (Community Atmosphere Model version 3.0, IsoCAM). A pre-industrial simulation was performed as the control experiment, as well as a simulation with all the boundary conditions set to Last Glacial Maximum (LGM) values. Results from the pre-industrial and LGM simulations were compared to experiments in which the influence of individual boundary conditions (greenhouse gases, ice sheet albedo and topography, sea surface temperature (SST), and orbital parameters) were changed each at a time to assess their individual impact. The experiments were designed in order to analyze the spatial variations of the oxygen isotopic composition of precipitation (d18Oprecip) in response to individual climate factors. The change in topography (due to the change in land ice cover) played a significant role in reducing the surface temperature and d18Oprecip over North America. Exposed shelf areas and the ice sheet albedo reduced the Northern Hemisphere surface temperature and d18Oprecip further. A global mean cooling of 4.1 °C was simulated with combined LGM boundary conditions compared to the control simulation, which was in agreement with previous experiments using the fully coupled Community Climate System Model (CCSM3). Large reductions in d18Oprecip over the LGM ice sheets were strongly linked to the temperature decrease over them. The SST and ice sheet topography changes were responsible for most of the changes in the climate and hence the d18Oprecip distribution among the simulations.

Color data, carbon and oxygen isotopes, and offsets from BBCP Polecat Bench cores 2A and 2B

The Earth's climate abruptly warmed by 5-8 °C during the Palaeocene-Eocene thermal maximum (PETM), about 55.5 million years ago**1,2. This warming was associated with a massive addition of carbon to the ocean-atmosphere system, but estimates of the Earth systemresponse to this perturbation are complicated by widely varying estimates of the duration of carbon release, which range from less than a year to tens of thousands of years. In addition the source of the carbon, and whether it was released as a single injection or in several pulses, remains the subject of debate**2-4. Here we present a new high-resolution carbon isotope record from terrestrial deposits in the Bighorn Basin (Wyoming, USA) spanning the PETM, and interpret the record using a carbon-cycle boxmodel of the ocean-atmosphere-biosphere system.Our record shows that the beginning of the PETMis characterized by not one but two distinct carbon release events, separated by a recovery to background values. To reproduce this pattern, our model requires two discrete pulses of carbon released directly to the atmosphere, at average rates exceeding 0.9 Pg C yr**-1, with the first pulse lasting fewer than 2,000 years.

Coral oxygen isotope and Sr/Ca data from the Northern Gulf of Aqaba (Red Sea)

The last interglacial period (about 125,000 years ago) is thought to have been at least as warm as the present climate (Kukla et al., 2002, doi:10.1006/qres.2001.2316). Owing to changes in the Earth's orbit around the Sun, it is thought that insolation in the Northern Hemisphere varied more strongly than today on seasonal timescales (Berger, 1987, doi:10.1175/1520-0469(1978)035<2362:LTVODI>2.0.CO;2), which would have led to corresponding changes in the seasonal temperature cycle (Montoya et al., 2000, doi:10.1175/1520-0442(2000)013<1057:CSFKBW>2.0.CO;2). Here we present seasonally resolved proxy records using corals from the northernmost Red Sea, which record climate during the last interglacial period, the late Holocene epoch and the present. We find an increased seasonality in the temperature recorded in the last interglacial coral. Today, climate in the northern Red Sea is sensitive to the North Atlantic Oscillation (Felis et al., 2000 doi:10.1029/1999PA000477; Rimbu et al., 2001, doi:10.1029/2001GL013083), a climate oscillation that strongly influences winter temperatures and precipitation in the North Atlantic region. From our coral records and simulations with a coupled atmosphere-ocean circulation model, we conclude that a tendency towards the high-index state of the North Atlantic Oscillation during the last interglacial period, which is consistent with European proxy records (Zagwijn, 1996, doi:10.1016/0277-3791(96)00011-X; Aalbersberg and Litt, 1998, doi:10.1002/(SICI)1099-1417(1998090)13:5<367::AID-JQS400>3.0.CO;2-I; Klotz et al., 2003, doi:10.1016/S0921-8181(02)00222-9), contributed to the larger amplitude of the seasonal cycle in the Middle East.

Oxygen isotopes and Sr/Ca ratios of fossil corals from Bonaire

Explanations for the demise of the Classic Maya civilization on the Yucatán Peninsula during the Terminal Classic Period (TCP; CE 750-1050) are controversial. Multiyear droughts are one likely cause, but the role of the Caribbean Sea, the dominant moisture source for Mesoamerica, remains largely unknown. Here we present bimonthly resolved snapshots of reconstructed sea surface temperature (SST) and salinity (SSS) variability in the southern Caribbean from precisely dated fossil corals. Our fossil coral results from Bonaire indicate strong interannual to decadal SST and SSS variability in the southern Caribbean Sea during the TCP with multiyear extremes of high SSS and high SST that coincide with droughts on the Yucatán Peninsula. The results are best explained by changed Caribbean SST gradients affecting the Caribbean low-level atmospheric jet with consequences for Mesoamerican precipitation, possibly linked to changes in Atlantic Meridional Overturning Circulation strength. Our findings provide a new perspective on the anomalous hydrological changes on the Yucatán Peninsula during the TCP that complement the often-suggested southward displacement of the Intertropical Convergence Zone. We advocate for a strong role of ocean-atmosphere interactions in the Caribbean Sea related to the multiyear variations in Caribbean Sea surface conditions as an important driver of the spatially complex pattern of hydrological anomalies during the TCP.

Oxygen and carbon isotope composition of Globoquadrina venezuelana and Oridorsalis umbonatus at DSDP Leg 85 Holes

Oxygen and carbon isotope stratigraphies are given for the planktonic foraminifer Globoquadrina venezuelana (a deep-dwelling species) at three DSDP sites located along a north-south transect at approximately 133°W across the Pacific equatorial high-productivity zone. The records obtained at Sites 573 and 574 encompass the lower Miocene. At Site 575 the record includes the middle Miocene and extends into the lowermost lower Miocene. The time resolution of the planktonic foraminifer isotope record varies from 50,000 to 500,000 yr. The benthic foraminifer Oridorsalis umbonatus was analyzed for isotope composition at a few levels of Site 575. Isotope stratigraphies for all three sites are compared with carbonate, foraminifer preservation, and grain size records. We identified a number of chemostratigraphic signals that appear to be synchronous with previously recognized signals in the western equatorial Pacific and the tropical Indian Ocean, and thus provide useful tools for chronostratigraphic correlations. The sedimentary sequence at Site 573 is incomplete and condensed, whereas the sequences from Sites 574 and 575 together provide a complete lower Miocene record. The expanded nature of this record, which was recovered with minimum disturbance and provides excellent calcareous and siliceous biostratigraphic control, offers a unique opportunity to determine the precise timing of early Miocene events. Paleomagnetic data from the hydraulic piston cores at Site 575 for the first time allow late early Miocene paleoceanographic events to be tied directly to the paleomagnetic time scale. The multiple-signal stratigraphies provide clues for paleoceanographic reconstruction during the period of preconditioning before the major middle Miocene cooling. In the lowermost lower Miocene there is a pronounced shift toward greater d13C values (by -1%) within magnetic Chron 16 (between approximately 17.5 and 16.5 Ma). The "Chron 16 Carbon Shift" coincides with the cessation of an early Miocene warming trend visible in the d18O signals. Values of d13C remain high until approximately 15 Ma, then decrease toward initial (early Miocene) values near 13.5 Ma. The broad lower to middle Miocene d13C maximum appears to correlate with the deposition of organic-carbon-rich sediments around the margin of the northern Pacific in the Monterey Formation of California and its lateral equivalents. The sediments rimming the Pacific were probably deposited under coastal upwelling conditions that may have resulted from the development of a strong permanent thermocline. Deposition in the upwelling areas occurred partly under anaerobic conditions, which led to the excess extraction of organic carbon from the ocean. The timing of the middle Miocene cooling, which began after the Chron 16 Carbon Shift, suggests that the extraction of organic carbon preconditioned the ocean-atmosphere system for subsequent cooling. A major carbonate dissolution event in the late early Miocene, starting at approximately 18.7 Ma, is associated with the enrichment in 13C. The maximum dissolution is coeval with the Chron 16 Carbon Shift. It corresponds to a prominent acoustic horizon that can be traced throughout the equatorial Pacific.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Southern Ocean

Recent evidence that dissolved organic carbon (DOC) is a significant component of the organic carbon flux below the photic layer of the ocean (1), together with verification of high respiration rates in the dark ocean (2), suggests that the downward flux of DOC may play a major role in supporting respiration there. Here we show, on the basis of examination of the relation between DOC and apparent oxygen utilization (AOU), that the DOC flux supports ~10% of the respiration in the dark ocean. The contribution of DOC to pelagic respiration below the surface mixed layer can be inferred from the relation between DOC and apparent oxygen utilization (AOU, µM O2), a variable quantifying the cumulative oxygen consumption since a water parcel was last in contact with the atmosphere. However, assessments of DOC/AOU relations have been limited to specific regions of the ocean (3, 4) and have not considered the global ocean. We assembled a large data set (N = 9824) of concurrent DOC and AOU observations collected in cruises conducted throughout the world's oceans (fig. S1, table S1) to examine the relative contribution of DOC to AOU and, therefore, respiration in the dark ocean. AOU increased from an average (±SE) 96.3 ± 2.0 µM at the base of the surface mixed layer (100 m) to 165.5 ± 4.3 µM at the bottom of the main thermocline (1000 m), with a parallel decline in the average DOC from 53.5 ± 0.2 to 43.4 ± 0.3 µM C (Fig. 1). In contrast, there is no significant decline in DOC with increasing depth beyond 1000 m depth (Fig. 1), indicating that DOC exported with overturning circulation plays a minor role in supporting respiration in the ocean interior (5). Assuming a molar respiratory quotient of 0.69, the decline in DOC accounts for 19.6 ± 0.4% of the AOU within the top 1000 m (Fig. 1). This estimate represents, however, an upper limit, because the correlation between DOC and AOU is partly due to mixing of DOC-rich warm surface waters with DOC-poor cold thermocline waters (6). Removal of this effect by regressing DOC against AOU and water temperature indicates that DOC supports only 8.4 ± 0.3% of the respiration in the mesopelagic waters.

Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.