Pigment data set from the SeaWiFS Bio-optical Archive and Storage System (1961-1996)

The oceans play a critical role in the Earth's climate, but unfortunately, the extent of this role is only partially understood. One major obstacle is the difficulty associated with making high-quality, globally distributed observations, a feat that is nearly impossible using only ships and other ocean-based platforms. The data collected by satellite-borne ocean color instruments, however, provide environmental scientists a synoptic look at the productivity and variability of the Earth's oceans and atmosphere, respectively, on high-resolution temporal and spatial scales. Three such instruments, the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) onboard ORBIMAGE's OrbView-2 satellite, and two Moderate Resolution Imaging Spectroradiometers (MODIS) onboard the National Aeronautic and Space Administration's (NASA) Terra and Aqua satellites, have been in continuous operation since September 1997, February 2000, and June 2002, respectively. To facilitate the assembly of a suitably accurate data set for climate research, members of the NASA Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) Project and SeaWiFS Project Offices devote significant attention to the calibration and validation of these and other ocean color instruments. This article briefly presents results from the SIMBIOS and SeaWiFS Project Office's (SSPO) satellite ocean color validation activities and describes the SeaWiFS Bio-optical Archive and Storage System (SeaBASS), a state-of-the-art system for archiving, cataloging, and distributing the in situ data used in these activities.

Average nutrient concentration, and growth characteristics of bacteria during USCGC Healy cruises in 2002 and 2004

Standing stocks and production rates for phytoplankton and heterotrophic bacteria were examined during four expeditions in the western Arctic Ocean (Chukchi Sea and Canada Basin) in the spring and summer of 2002 and 2004. Rates of primary production (PP) and bacterial production (BP) were higher in the summer than in spring and in shelf waters than in the basin. Most surprisingly, PP was 3-fold higher in 2004 than in 2002; ice-corrected rates were 1581 and 458 mg C/m**2/d respectively, for the entire region. The difference between years was mainly due to low ice coverage in the summer of 2004. The spatial and temporal variation in PP led to comparable variation in BP. Although temperature explained as much variability in BP as did PP or phytoplankton biomass, there was no relationship between temperature and bacterial growth rates above about 0°C. The average ratio of BP to PP was 0.06 and 0.79 when ice-corrected PP rates were greater than and less than 100 mg C/m**2/d, respectively; the overall average was 0.34. Bacteria accounted for a highly variable fraction of total respiration, from 3% to over 60% with a mean of 25%. Likewise, the fraction of PP consumed by bacterial respiration, when calculated from growth efficiency (average of 6.9%) and BP estimates, varied greatly over time and space (7% to >500%). The apparent uncoupling between respiration and PP has several implications for carbon export and storage in the western Arctic Ocean.

Bulk sedimentology from Sites M0002 and M0004 of the ACEX (Exp302) expedition to the Arctic Ocean

Except for a few discontinuous fragments of the Late Cretaceous/Early Cenozoic climate history and depositional environment, the paleoenvironmental evolution of the pre-Neogene central Arctic Ocean was virtually unknown prior to the IODP Expedition 302 (Arctic Ocean Coring Expedition - ACEX) drilling campaign on Lomonosov Ridge in 2004. Here we present detailed organic carbon (OC) records from the entire ca. 200 m thick Paleogene OC-rich section of the ACEX drill sites. These records indicate euxinic "Black Sea-type" conditions favorable for the preservation of labile aquatic (marine algae-type) OC occur throughout the upper part of the early Eocene and the middle Eocene, explained by salinity stratification due to freshwater discharge. The superimposed short-term ("Milankovitch-type") variability in amount and composition of OC is related to changes in primary production and terrigenous input. Prominent early Eocene events of algae-type OC preservation coincide with global d13C events such as the PETM and Elmo events. The Elmo d13C Event has been identified in the Arctic Ocean for the first time.

Organic-geochemical and petrographical composition of sediments from ODP Leg 164 sites

Sediments from Holes 994C, 995A, 997A, and 997B have been investigated for "combined" gases (adsorbed gas and that portion of free gas that has not escaped from the pore volume during core recovery and sample collection and storage), solvent-extractable organic compounds, and microscopically identifiable organic matter. The soluble materials mainly consist of polar compounds. The saturated hydrocarbons are dominated by n-alkanes with a pronounced odd-even predominance pattern that is derived from higher plant remains. Unsaturated triterpenoids and 17ß, 21ß-pentacyclic triterpenoids are characteristic for a low maturity stage of the organic matter. The low maturity is confirmed by vitrinite reflectance values of 0.3%. The proportion of terrestrial remains (vitrinite) increases with sub-bottom depth. Within the liptinite fraction, marine algae plays a major role in the sections below 180 mbsf, whereas above this depth sporinites and pollen from conifers are dominant. These facies changes are confirmed by the downhole variations of isoprenoid and triterpenoid ratios in the soluble organic matter. The combined gases contain methane, ethane, and propane, which is a mixture of microbial methane and thermal hydrocarbon gases. The variations in the gas ratios C1/(C2+C3) reflect the depth range of the hydrate stability zone. The carbon isotopic contents of ethane and propane indicate an origin from marine organic matter that is in the maturity stage of the oil window.

Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.

(Table 1) Carbon pools in different vegetation components in grazed and ungrazed plots near Ny-Ålesund, Spitzbergen

The carbon (C) sink strength of arctic tundra is under pressure from increasing populations of arctic breeding geese. In this study we examined how CO2 and CH4 fluxes, plant biomass and soil C responded to the removal of vertebrate herbivores in a high arctic wet moss meadow that has been intensively used by barnacle geese (Branta leucopsis) for ca. 20 years. We used 4 and 9 years old grazing exclosures to investigate the potential for recovery of ecosystem function during the growing season (July 2007). The results show greater above- and below-ground vascular plant biomass within the grazing exclosures with graminoid biomass being most responsive to the removal of herbivory whilst moss biomass remained unchanged. The changes in biomass switched the system from net emission to net uptake of CO2 (0.47 and -0.77 µmol/m**2/s in grazed and exclosure plots, respectively) during the growing season and doubled the C storage in live biomass. In contrast, the treatment had no impact on the CH4 fluxes, the total litter C pool or the soil C concentration. The rapid recovery of the above ground biomass and CO2 fluxes demonstrates the plasticity of this high arctic ecosystem in terms of response to changing herbivore pressure.

Effects of high temperature and CO2 on intracellular DMSP in the cold-water coral Lophelia pertusa

Significant warming and acidification of the oceans is projected to occur by the end of the century. CO2 vents, areas of upwelling and downwelling, and potential leaks from carbon capture and storage facilities may also cause localised environmental changes, enhancing or depressing the effect of global climate change. Cold-water coral ecosystems are threatened by future changes in carbonate chemistry, yet our knowledge of the response of these corals to high temperature and high CO2 conditions is limited. Dimethylsulphoniopropionate (DMSP), and its breakdown product dimethylsulphide (DMS), are putative antioxidants that may be accumulated by invertebrates via their food or symbionts, although recent research suggests that some invertebrates may also be able to synthesise DMSP. This study provides the first information on the impact of high temperature (12 °C) and high CO2 (817 ppm) on intracellular DMSP in the cold-water coral Lophelia pertusa from the Mingulay Reef Complex, Scotland (56°49' N, 07°23' W), where in situ environmental conditions are meditated by tidally induced downwellings. An increase in intracellular DMSP under high CO2 conditions was observed, whilst water column particulate DMS + DMSP was reduced. In both high temperature treatments, intracellular DMSP was similar to the control treatment, whilst dissolved DMSP + DMS was not significantly different between any of the treatments. These results suggest that L. pertusa accumulates DMSP from the surrounding water column; uptake may be up-regulated under high CO2 conditions, but mediated by high temperature. These results provide new insight into the biotic control of deep-sea biogeochemistry and may impact our understanding of the global sulphur cycle, and the survival of cold-water corals under projected global change.

(Table 1) CPI17-23, hopanoic acid, and n-C35 + lycopane/n-C31 ratios as well as 17beta(H), 21beta(H) homohopane, long-chain alkanes, and alkenones concentrations in IODP Exp302

During Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition (ACEX)) a more than 200 m thick sequence of Paleogene organic carbon (OC)-rich (black shale type) sediments was drilled. Here we present new biomarker data determined in ACEX sediment samples to decipher processes controlling OC accumulation and their paleoenvironmental significance during periods of Paleogene global warmth and proposed increased freshwater discharge in the early Cenozoic. Specific source-related biomarkers including n-alkanes, fatty acids, isoprenoids, carotenoids, hopanes/hopenes, hopanoic acids, aromatic terpenoids, and long-chain alkenones show a high variability of components, derived from marine and terrestrial origin. The distribution of hopanoic acid isomers is dominated by compounds with the biological 17beta(H), 21beta(H) configuration indicating a low level of maturity. On the basis of the biomarker data the terrestrial OC supply was significantly enriched during the late Paleocene and part of the earliest Eocene, whereas increased aquatic contributions and euxinic conditions of variable intensity were determined for the Paleocene-Eocene thermal maximum and Eocene thermal maximum 2 events as well as the middle Eocene time interval. Furthermore, samples from the middle Eocene are characterized by the occurrence of long-chain alkenones, high proportions of lycopane, and high ratios (>0.6) of (n-C35 + lycopane)/n-C31. The occurrence of C37-alkenenones, which were first determined toward the end of the Azolla freshwater event, indicates that the OC becomes more marine in origin during the middle Eocene. Preliminary UK'37- based sea surface temperature (SST) values display a longterm temperature decrease of about 15C during the time interval 49-44.5 Ma (25° to 10°C), coinciding with the global benthic d18O cooling trend after the early Eocene climatic optimum. At about 46 Ma, parallel with onset of ice-rafted debris, SST (interpreted as summer temperatures) decreased to values <15°C. For the late early Miocene a SST of 11°-15°C was determined. Most of the middle Eocene ACEX sediments are characterized by a smooth short-chain n-alkane distribution, which may point to natural oil-type hydrocarbons from leakage of petroleum reservoirs or erosion of related source rocks and redeposition.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

(Table 1) Elemental mean values of the upper Paleocene and lower Eocene in IODP Hole 302-M0004A

We reconstruct the latest Paleocene and early Eocene (~57-50 Ma) environmental trends in the Arctic Ocean and focus on the Paleocene-Eocene thermal maximum (PETM) (~55 Ma), using strata recovered from the Lomonosov Ridge by the Integrated Ocean Drilling Program Expedition 302. The Lomonosov Ridge was still partially subaerial during the latest Paleocene and earliest Eocene and gradually subsided during the early Eocene. Organic dinoflagellate cyst (dinocyst) assemblages point to brackish and productive surface waters throughout the latest Paleocene and early Eocene. Dinocyst assemblages are cosmopolitan during this time interval, suggesting warm conditions, which is corroborated by TEX86'-reconstructed temperatures of 15°-18°C. Inorganic geochemistry generally reflects reducing conditions within the sediment and euxinic conditions during the upper lower Eocene. Spectral analysis reveals that the cyclicity, recorded in X-ray fluorescence scanning Fe data from close to Eocene thermal maximum 2 (~53 Ma, presence confirmed by dinocyst stratigraphy), is related to precession. Within the lower part of the PETM, proxy records indicate enhanced weathering, runoff, anoxia, and productivity along with sea level rise. On the basis of total organic carbon content and variations in sediment accumulation rates, excess organic carbon burial in the Arctic Ocean appears to have contributed significantly to the sequestration of injected carbon during the PETM.

Chemistry and grain-size distribution of terrigenous sediments deposited at Site GeoB9501

The Sahara Desert is the largest source of mineral dust in the world. Emissions of African dust increased sharply in the early 1970s, a change that has been attributed mainly to drought in the Sahara/Sahel region caused by changes in the global distribution of sea surface temperature. The human contribution to land degradation and dust mobilization in this region remains poorly understood, owing to the paucity of data that would allow the identification of long-term trends in desertification. Direct measurements of airborne African dust concentrations only became available in the mid-1960s from a station on Barbados and subsequently from satellite imagery since the late 1970s: they do not cover the onset of commercial agriculture in the Sahel region ~170 years ago. Here we construct a 3,200-year record of dust deposition off northwest Africa by investigating the chemistry and grain-size distribution of terrigenous sediments deposited at a marine site located directly under the West African dust plume. With the help of our dust record and a proxy record for West African precipitation we find that, on the century scale, dust deposition is related to precipitation in tropical West Africa until the seventeenth century. At the beginning of the nineteenth century, a sharp increase in dust deposition parallels the advent of commercial agriculture in the Sahel region. Our findings suggest that human-induced dust emissions from the Sahel region have contributed to the atmospheric dust load for about 200 years.