Isotope characterisation of Villars Cave stalagmites

We present a new mid-latitude speleothem record of millennial-scale climatic variability during OIS3 from the Villars Cave that, combined with former published contemporaneous samples from the same cave, gives a coherent image of the climate variability in SW-France between ~55 ka and ~30 ka. The 0.82 m long stalagmite Vil-stm27 was dated with 26 TIMS U-Th analyses and its growth curve displays variations that are linked with the stable isotopes, both controlled by the climatic conditions. It consists in a higher resolved replicate of the previously published Vil-stm9 and Vil-stm14 stalagmites where Dansgaard-Oeschger (DO) events have been observed. The good consistency between these three stalagmites and the comparison with other palaoeclimatic reconstructions, especially high resolution pollen records (ODP 976 from the Alboran Sea, Monticchio Lake record from southern Italy) and the nearby MD04-2845 Atlantic Ocean record, permits to draw a specific climatic pattern in SW-France during the OIS3 and to see regional differences between these sites. Main features of this period are: 1) warm events corresponding to Greenland Interstadials (GIS) that are characterized by low speleothem d13C, high temperate pollen percentages, warm temperatures and high humidity; among these events, GIS#12 is the most pronounced one at Villars characterized by an abrupt onset at ~46.6 ka and a duration of about 2.5 ka. The other well individualized warm event coincides with GIS#8 which is however much less pronounced and occurred during a cooler period as shown by a lower growth rate and a higher d13C; 2) cold events corresponding to Greenland Stadials (GS) that are clearly characterized by high speleothem d13C, low temperate pollen abundance, low temperature and enhanced dryness, particularly well expressed during GS coinciding with Heinrich events H5 and H4. The main feature of the Villars record is a general cooling trend between the DO#12 event ~45.5 ka and the synchronous stop of the three stalagmites at ~30 ka ±1, with a first well marked climatic threshold at ~41 ka after which the growth rate and the diameter of all stalagmites slows down significantly. This climatic evolution differs from that shown at southern Mediterranean sites where this trend is not observed. The ~30 ka age marks the second climatic threshold after which low temperatures and low rainfalls prevent speleothem growth in the Villars area until the Lateglacial warming that occurred at ~16.5 ± 0.5 ka. This 15 ka long hiatus, as the older Villars growth hiatus that occurred between 67.4 and 61 ka, are linked to low sea levels, reduced ocean circulation and a southward shift of the Polar Front that likely provoked local permafrost formation. These cold periods coincide with both low summer 65°N insolation, low atmospheric CO2 concentration and large ice sheets development (especially the Fennoscandian).

Neogene ice-rafted debris record of ODP Hole 120-751A

One of the primary objectives of Leg 120 was to obtain a high-resolution Neogene stratigraphic section from the Kerguelen Plateau. Site 751, located in the central part of the Raggatt Basin on the Southern Kerguelen Plateau in 1633.8 m of water (57°43.56'S; 79°48.89'E), was selected as the dedicated Neogene site for this objective. High-resolution sampling at Site 751 was used to delineate in detail the Neogene ice-rafted debris (IRD) occurrences on the Kerguelen Plateau. The oldest IRD found at Site 751 was approximately 9.9 Ma, and it was not until approximately 8.5 Ma that significant concentrations of IRD were detected. The first major IRD event at this site occurred in the uppermost Miocene between 6.0 and 5.5 Ma. During this time period, a general climatic cooling and glacial expansion occurred on Antarctica. The late Miocene IRD event was followed by a continuous episode of elevated IRD deposition in the lowermost Pliocene between 4.5 and 4.1 Ma. The 0.4-m.y. duration and the timing of the early Pliocene IRD event on the Kerguelen Plateau corresponds with IRD fluxes observed on the Falkland Plateau and in the Weddell Abyssal Plain. This correspondence of data indicates that a major global climatic event occurred during the early Pliocene. The East Antarctic Ice Sheet may have experienced deglaciation between 4.5 and 4.1 Ma and, as a result, released large volumes of sediment-laden ice into the Southern Ocean.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Wetland maps including open water extent dynamics based on ENVISAT ASAR WS for Siberia, 2007 and 2008, links to GeoTIFFs

Wetlands store large amounts of carbon, and depending on their status and type, they release specific amounts of methane gas to the atmosphere. The connection between wetland type and methane emission has been investigated in various studies and utilized in climate change monitoring and modelling. For improved estimation of methane emissions, land surface models require information such as the wetland fraction and its dynamics over large areas. Existing datasets of wetland dynamics present the total amount of wetland (fraction) for each model grid cell, but do not discriminate the different wetland types like permanent lakes, periodically inundated areas or peatlands. Wetland types differently influence methane fluxes and thus their contribution to the total wetland fraction should be quantified. Especially wetlands of permafrost regions are expected to have a strong impact on future climate due to soil thawing. In this study ENIVSAT ASAR Wide Swath data was tested for operational monitoring of the distribution of areas with a long-term SW near 1 (hSW) in northern Russia (SW = degree of saturation with water, 1 = saturated), which is a specific characteristic of peatlands. For the whole northern Russia, areas with hSW were delineated and discriminated from dynamic and open water bodies for the years 2007 and 2008. The area identified with this method amounts to approximately 300,000 km**2 in northern Siberia in 2007. It overlaps with zones of high carbon storage. Comparison with a range of related datasets (static and dynamic) showed that hSW represents not only peatlands but also temporary wetlands associated with post-forest fire conditions in permafrost regions. Annual long-term monitoring of change in boreal and tundra environments is possible with the presented approach. Sentinel-1, the successor of ENVISAT ASAR, will provide data that may allow continuous monitoring of these wetland dynamics in the future complementing global observations of wetland fraction.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Pore-water chemistry of abyssal Arabian Sea surface sediments

Benthic fluxes and pore-water compositions of silicic acid, nitrate and phosphate were investigated for surface sediments of the abyssal Arabian Sea during four cruises (1995-1998). Five sites located in the northern (NAST), western (WAST), central (CAST), eastern (EAST), and southern (SAST) Arabian Sea were revisited during intermonsoonal periods after the NE- and SW-Monsoon. At these sites, benthic fluxes of remineralized nutrients from the sediment to the bottom water of 36-106, 102-350 and 4-16 mmol/m**2/yr were measured for nitrate, silicic acid and phosphate, respectively. The benthic fluxes and pore-water compositions showed a distinct regional pattern. Highest fluxes were observed in the western and northern region of the Arabian Sea, whereas decreasing fluxes were derived towards the southeast. At WAST, the general temporal pattern of primary production, related to the NE- and SW-Monsoon, is reflected by benthic fluxes. In contrast, at sites NAST, SAST, CAST, and EAST a temporal pattern of fluxes in response to the monsoon is not obvious. Our results reveal a clear coupling between the general regional pattern of production in surface waters and the response of the benthic environment, as indicated by the flux of remineralized nutrients, though a spatially differing degree of decoupling during transport and remineralization of particulate organic matter and biogenic opal was observed. This has to be taken into account regarding budget calculations and paleoceanographic topics.

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

Concentrations of total organic carbon (TOC) were determined on samples collected during six cruises in the northern Arabian Sea during the 1995 US JGOFS Arabian Sea Process Study. Total organic carbon concentrations and integrated stocks in the upper ocean varied both spatially and seasonally. Highest mixed-layer TOC concentrations (80-100 µM C) were observed near the coast when upwelling was not active, while upwelling tended to reduce local concentrations. In the open ocean, highest mixed-layer TOC concentrations (80-95 µM C) developed in winter (period of the NE Monsoon) and remained through mid summer (early to mid-SW Monsoon). Lowest open ocean mixed-layer concentrations (65-75 µM C) occurred late in the summer (late SW Monsoon) and during the Fall Intermonsoon period. The changes in TOC concentrations resulted in seasonal variations in mean TOC stocks (upper 150 m) of 1.5-2 mole C/m**2, with the lowest stocks found late in the summer during the SW Monsoon-Fall Intermonsoon transition. The seasonal accumulation of TOC north of 15°N was 31-41 x 10**12 g C, mostly taking place over the period of the NE Monsoon, and equivalent to 6-8% of annual primary production estimated for that region in the mid-1970s. A net TOC production rate of 12 mmole C/m**2/d over the period of the NE Monsoon represented ~80% of net community production. Net TOC production was nil during the SW Monsoon, so vertical export would have dominated the export terms over that period. Total organic carbon concentrations varied in vertical profiles with the vertical layering of the water masses, with the Persian Gulf Water TOC concentrations showing a clear signal. Deep water (>2000 m) TOC concentrations were uniform across the basin and over the period of the cruises, averaging 42.3±1.4 µM C.

Organic geochemical character and hydrocarbon source potential of selected black shales at DSDP Hole 93-603B

LECO analysis, pyrolysis assay, and bitumen and elemental analysis were used to characterize the organic matter of 23 black shale samples from Deep Sea Drilling Project Leg 93, Hole 603B, located in the western North Atlantic. The organic matter is dominantly gas-prone and/or refractory. Two cores within the Turonian and Cenomanian, however, contained significant quantities of well-preserved, hydrogen-enriched, organic matter. This material is thermally immature and represents a potential oil-prone source rock. These sediments do not appear to have been deposited within a stagnant, euxinic ocean as would be consistent with an "oceanic anoxic event." Their organic geochemical and sedimentary character is more consistent with deposition by turbidity currents originating on the continental shelf and slope.

Stable isotope record and distribution of foraminifera in sediment core GeoB3004-1

Fluctuations in the abundance of selected foraminiferal indicator species and diversity allowed the reconstruction of changes in deepwater oxygenation and monsoon-driven organic matter fluxes in the deep western Arabian Sea during the last 190 kyr. Times of maximum surface production coincide with periods of intensified SW monsoon as shown by the abundance of Globigerina bulloides and enhanced carbonate corrosion. Benthic ecosystem variability in the deep Arabian Sea is not exclusively driven by variations in monsoonal upwelling and related organic matter supply to the seafloor but also by changes in deepwater ventilation. Deepening of the base of the oxygen minimum zone (OMZ) below 1800 m water depth is strongly coherent on the precessional band but lags proxies of SW monsoon strength by 4 to 6 kyr. The "out-of-phase" relationship between OMZ deepening and maximum SW monsoon strength is explained by temporal changes in the advection of oxygen-rich deepwater masses of North Atlantic and Antarctic origin. This process affected the remineralization and burial efficiency of organic matter in the deep Arabian Sea, resulting in the observed phase lag between maximum monsoon strength and organic carbon preservation.

Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.

Pliocene foraminifera and SST changes in ODP Site 184-1125

Planktonic foraminiferal census counts were converted to sea surface temperature (SST) estimates using the modern analogue technique (MAT) for the middle-late Pliocene (4.0-2.37 Ma) in ODP Site 1125, north side of Chatham Rise, SW Pacific Ocean. MAT SST(warm) records range between 8°C and 20.5°C, and MAT SST(cold) records parallel that pattern but with a temperature range of 5-15°C. The modern position of Site 1125 is just north of the Subtropical Front and has an annual temperature range of ~14-18°C. Pliocene warmest temperatures are 1-2° warmer than modern summers, whereas cold season SST records are up to 6-10°C cooler than modern winters. Overall average temperatures at the site are 2-3°C cooler than modern temperatures during a time of sustained global warmth. Three major cold excursions centred on 3.35, 3.0, and 2.8 Ma showed warm season temperatures over 5°C colder than the last glacial maximum, experiencing temperatures typical of modern subantarctic waters. Two minor cold excursions at 2.7 Ma and 2.4 Ma experienced temperatures cooler than modern winters but not as cold as last glacial conditions. Cold season SSTs show a shift to warmer climate upward through the study interval, whereas warm season estimates remain essentially unchanged. We interpret the strong regional cooling of subtropical Southwest Pacific water through the middle-late Pliocene as having been caused by increased upwelling. It is also possible that the subtropical frontal zone moved north over the site in the Pliocene, however, this is considered the least likely interpretation. Our record of cool conditions in the Southwest Pacific corroborate evidence of cooler than modern conditions in other regions of the western Pacific through the mid-Pliocene despite overall global warming.