Halogene concentrations and iodine isotopic composition in pore water on Hydrare Ridge, Cascadia continental margin

We report iodine and bromine concentrations in a total of 256 pore water samples collected from all nine sites of Ocean Drilling Program Leg 204, Hydrate Ridge. In a subset of these samples, we also determined iodine ages in the fluids using the cosmogenic isotope 129I (T1/2 = 15.7 Ma). The presence of this cosmogenic isotope, combined with the strong association of iodine with methane, allows the identification of the organic source material responsible for iodine and methane in gas hydrates. In all cores, iodine concentrations were found to increase strongly with depth from values close to that of seawater (0.0004 mM) to concentrations >0.5 mM. Several of the cores taken from the northwest flank of the southern summit show a pronounced maximum in iodine concentrations at depths between 100 and 150 meters below seafloor in the layer just above the bottom-simulating reflector. This maximum is especially visible at Site 1245, where concentrations reach values as high as 2.3 mM, but maxima are absent in the cores taken from the slope basin sites (Sites 1251 and 1252). Bromine concentrations follow similar trends, but enrichment factors for Br are only 4-8 times that of seawater (i.e., considerably lower than those for iodine). Iodine concentrations are sufficient to allow isotope determinations by accelerator mass spectrometry in individual pore water samples collected onboard (~5 mL). We report 129I/I ratios in a few samples from each core and a more complete profile for one flank site (Site 1245). All 129I/I ratios are below the marine input ratio (Ri = 1500x10**-15). The lowest values found at most sites are between 150 and 250x10**-15, which correspond to minimum ages between 40 and 55 Ma, respectively. These ages rule out derivation of most of the iodine (and, by association, of methane) from the sediments hosting the gas hydrates or from currently subducting sediments. The iodine maximum at Site 1245 is accompanied by an increase in 129I/I ratios, suggesting the presence of an additional source with an age younger than 10 Ma; there is indication that younger sources also contribute at other sites, but data coverage is not yet sufficient to allow a definitive identification of sources there. Likely sources for the older component are formations of early Eocene age close to the backstop in the overriding wedge, whereas the younger sources might be found in recent sediments underlying the current locations of the gas hydrates.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Terrigenous sedimentation of sediment core GeoB6007-2

Variations in deposition of terrigenous fine sediments and their grain-size distributions from a high-resolution marine sediment record offshore northwest Africa (30°51.0'N; 10°16.1'W) document climate changes on the African continent during the Holocene. End-member grain-size distributions of the terrigenous silt fraction, which are related to fluvial and aeolian dust transport, indicate millennial-scale variability in the dominant transport processes at the investigation site off northwest Africa as well as recurring periods of dry conditions in northwest Africa during the Holocene. The terrigenous record from the subtropical North Atlantic reflects generally humid conditions before the Younger Dryas, during the early to mid-Holocene, as well as after 1.3 kyr BP. By contrast, continental runoff was reduced and arid conditions were prevalent at the beginning of the Younger Dryas and during the mid- and late Holocene. A comparison with high- and low-latitude Holocene climate records reveals a strong link between northwest African climate and Northern Hemisphere atmospheric circulation throughout the Holocene. Due to its proximal position, close to an ephemeral river system draining the Atlas Mountains as well as the adjacent Saharan desert, this detailed marine sediment record, which has a temporal resolution between 15 and 120 years, is ideally suited to enhance our understanding of ocean-continent-atmosphere interactions in African climates and the hydrological cycle of northern Africa after the last deglaciation.

Pollen records and lithology of profiles from Lobsigensee, Switzerland

Lobsigensee is a small kettle hole lake 15 km north-west of Bern on the Swiss Plateau, at an altitude of 514 m asl. Its surface is 2ha today, its maximum depth 2.7 m; it has no inlet and the overflow functions mainly during snow melting. The area was covered by Rhone ice during the Last Glaciation (map in Fig.2). Local geology, climate and vegetation are summarized in Figure 3A-C, the history of settlement in Figures 5-7. In order to reconstruct the vegetational and environmental history of the lake and its surroundings pollen analysis and other bio- and isotope stratigraphies were applied to twelve profiles cored across the basin with modified Livingstone corers (Fig.3 D). (1) The standard diagram: The central core LQ-90 is described as the standard pollen diagram (Chapter 3) with 10 local pollen assemblage zones of the Late-Glacial (local PAZ Ll to Ll0, from about 16'000(7) to 10'000 years BP) and 20 PAZ of the Holocene (local PAZ L11 to L30), see Figs. 8-10 and 20-24. Local PAZ L 1 to L3 are in the Late-Glacial clay and record the vegetational development after the ice retreat: L1 shows very low pollen concentration and high Pinus percentages due to long-distance transport and reworking; the latter mechanism is corroborated by the findings of thermophilous and pre-Quaternary taxa. Local PAZ L2 has a high di versi ty of non-arboreal pollen (NAP) and reflects the Late-Glacial steppe rich in heliophilous species. Local PAZ L3 is similar but additionally rich in Betula nana and Sal1x, thus reflecting a "shrub tundra". The PAZ L1 to L3 belong to the Oldest Dryas biozone. Local PAZ L4 to L 10 are found in the gyttja of the profundal or in the lake marl of the littoral and record the Late-Glacial forests. L4 is the shrub phase of reforestation with very high Junlperus and rapidly increasing Betula percentages. L5 is the PAZ with a first, L7 with a second dominance of tree-birches, separated by L6 showing a depression in the Betula curve. L4 to L7 can be assigned to the Balling biozone. Possible correlation of the Betula depression to the Older Dryas biozone is discussed. In local PAZ L8 Plnus immigrates and expands. L9 shows a facies difference in that Plnus dominates over Betula in littoral but not in profundal spectra. L8 and L9 belong to the Allerod biozone. In its youngest part the volcanic ash from Laach/Eifel is regularly found (11,000 BP). The local PAZ Ll0 corresponds to the Younger Dryas blozone. The merely slight increase of the NAP indicates that the pine forests of the lowland were not strongly affected by a cooler climate. In order to evaluate the significance of the littoral accumulation of coniferous pollen the littoral profile LQ-150 is compared to the profundal. Radiocarbon stratigraphies derived from different materials are presented in Figures 13 and 14 and in Tables 2 and 3. The hard-water errors in the gyttja samples and the carbonate samples are similar. The samples of terrestrial plant macrofossils are not affected by hard-water errors. Two plateaux of constant age appear in the age-depth relationship; their consequence for biostratigraphy as well as pollen concentration and influx diagrams are discussed. Radiocarbon ages of the Late-Glacial pollen zones are shown in Table 10. The Holocene vegetational history is recorded in the local PAZ L 11 to L30. After a Preboreal (PAZ L11) dominated by pine and birch the expansions of Corylus, Ulmus and Quercus are very rapid. Among these taxa Corylus dominates dur ing the Boreal (PAZ L 12 and L 1 3), whereas the components of the mixed oak forest dominate in the Older Atlantic (PAZ L14 to L16). In the Younger Atlantic (PAZ L 17 to L 19) Fagus and Alnus play an increasing, the mixed oak forest a decreasing role. During the period of local PAZ L19 Neolithic settlers lived on the shore of Lobsigensee. During the Subboreal (PAZ L20 and L21) and the Older Subatlantic (L22 to L25) strong fluctuations of Fagus and often antagonistic peaks of NAP, Alnus, Betula and Corylus can be interpreted as signs of human impact on vegetation. L23 is characterized not only by high values of NAP (especially apophytes and anthropochorous species) but also by the appearance of Juglans, Castanea and Secale which point to the Roman colonization of the area. For a certain period during the Younger Subatlantic (PAZ L26 to L30) the lake was used for retting hemp (Cannabis). Later the dominance of Quercus pollen indicates the importance of wood pastures. The youngest sediments reflect the wide-spread agricultural grass lands and the plantation of Pinus and Picea. Radiocarbon dates for the Holocene are given in Figure 23 and Table 4, the extrapolated ages of the Holocene pollen zones in Table 15. (2) The cross sections: Figures 25 and 26 give a summary of the litho- and palynostratigraphy of the two cross sections. Based on 11 Late-Glacial and 9 Holocene pollen diagrams (in addition to the standard ones), the consistency of the criteria for the definition of the pollen zones is examined in Tables 7 and 8 for the Late-Glacial and in Tables 11 to 14 for the Holocene. Sediment thicknesses across the basin for each pollen zone are presented in these tables as well as in Figures 43 to 45 for the Late-Glacial and in Figures 59 to 65 for the Holocene. Sediment focusing can explain differences between the gyttja cores of the profundal. Focusing is more than compensated for through "stretching" by carbonate precipitation on the littoral terrace. Pollen influx to the cross section are discussed (Chapters 4.1.5. and 4.2.3.). (3) The regional pollen zones: Based on some selected sites between Lake Geneva and Lake Constance regional pollen zones are proposed (Table 16, 17 and 19). (4) Paleoecology: Climatic change in the Late-Glacial can be inferred from Coleoptera, Trichoptera, Chironomidae and d18O of carbonates: a distinct warming is recorded around 12' 600 BP and around 10' 000 BP. The Younger Dryas biozone (10'700-10'000 BP) was the only cooling found in the Late-Glacial. The Betula depression often correlated wi th the Older Dryas biozone was possibl not colder but dryer than the previous period. During the Holocene the lowland site is not very sensitive to the minor climatic changes. Table 22 summarizes climatic and trophic changes before 8'000 BP as deduced from various biostratigraphies studied by a number of authors. Ostracods, Chironomids and fossil pigments indicate that anoxic conditions prevailed during the BoIling (possibly meromixis). Changes in the lake level are illustrated in Figure 74. A first lake-level lowering occurred in the early Holocene (10'000 to 9'000 BP), a second during the Atlantic (about 6'800 to 5'200 BP). The first "shrinking" of the lake volume resulted in a eutrophication recorded by laminations in the profundal and by pigments of Cyanophyceae. The second fall in water level corresponds to an increase of Nymphaeaceae. Human impact can be inferred in three ways: eutrophication of the lake (since the Neolithic), changes of terrestrial vegetation by deforestations (cyclicity of Fagus, see Figures 78 to 80), and enhanced erosion (increasing sedimentation rates by inwashed clay, particularly since the Roman Colonization, see Figures 49 and 81). Summary: This paper was planned as the final report on Lobsigensee. However, a number of issues are not answered but can only be asked more precisely, for example: (1) For the two periods with the highest rates of change, Le. the Bolling and the Preboreal biozones, pollen influx may reflect vegetation dynamics. Detailed investigations of these periods in annually laminated sediments are planned. (2) Biostratigraphies other than palynostratigraphy are needed to estimate the degree of linkage or independence in the development of terrestrial and lacustrine ecosystems. Often our sampling intervals were not identical, thus influencing our temporal resolution. (3) 6180- and 14C-stratigraPhies with high resolution will elucidate the leads and lags of these dynamic periods. Plateaux of constant age in the age-depth relationship have a strong bearing on both biological and geophysical understanding of Late-Glacial and early Holocene developments. (4) Numerical methods applied to the pollen diagrams of the cross section will help to quantify the significance of similari ties and dissimilarities across a single basin (with Prof. Birks). (5) Numerical methods applied to different sites on the Swiss Plateau and on the transect across the Alps will be helpful in evaluating the influence of different environmental factors (with Prof. Birks). (6) A new map 1: 1000 with 50cm-contour lines prov ided by Prof. Zurbuchen will be combined with a grid of cores sampling the transition from lake marl to peat enabling us to calculate paleo-volumes of the lake. This is interesting for the two "shrinking periods" (in Fig. 74A numbers 2-6 and 7-10), both accompanied by eutrophication. The pal eo-volume during the Neoli thic set tlement of the Cortaillod culture linked wi th an est l.mate of trophic change derived from diatoms (Prof. Smol in prep.) could possibly give an indication of the size of the human population of this period. (7) For the period with the antagonism between Fagus peaks and ABC-peaks close collaboration between palynologists, geochemists and archeologists should enable us to determine the influence of prehistoric and historic people on vegetation (collaboration with Prof. Stockli and Prof. Herzig). (8) The core LL-75 taken with a "cold letter box" will be analysed for major and trace elements by Dr. Sturm for 210pb and 137Cs by Prof.von Gunten and for pollen. We will see if our local PAZ L30 really corresponds to the surface sediment and if the small seepage lake reflects modern pollution.

Sea-surface temperature reconstruction of sediment core JT96-09PC

Changes of sea surface temperature (SST) in the subarctic NE Pacific over the last 16,000 calendar years before present (16 kyr BP) have been inferred from the study of C37 alkenone unsaturation in a sediment core from the western Canadian continental slope. Between 16.0 and 11.0 kyr, three distinct cold phases (6-7°C) interrupt two warmer periods (9-10°C). Within the 2sigma range of the radiocarbon based time control, the observed SST oscillations correspond to the Oldest Dryas, the Bolling, the Older Dryas, the Allered, and the Younger Dryas periods in the GISP2 d180 record. These results represent the first high resolution marine paleotemperature estimates off the northern West coast of North America and imply that the climate of this region may be very strongly coupled to that of the North Atlantic. Given the fast rates of SST change (1°C/40-80 yr), such coupling must be controlled by atmospheric transmission of the climate signal.

Barium in sediments off northwest Africa

High-resolution down-core analyses of the solid phase content of total barium (Batot) and total organic carbon (TOC) back to 25 kyr B.P. were performed on a gravity core from the upper continental slope off Cape Yubi (Morocco). The observed discrepancy between the two potential paleoproductivity proxies, Batot and TOC, initiated supplementary examinations of the pore water, the geochemistry of the clay fraction, X-ray diffraction analyses, and the application of a sequential Ba extraction method of selected samples. Additionally, we analyzed down-core samples of the planktonic foraminifera Turborotalita quinqueloba and Globorotalia inflata for their Ba/Ca ratios. These analyses, which were performed for the first time on these species, were used to reconstruct past oceanic Ba concentrations. We suggest that in the study area, which is characterized by high accumulation rates, the preserved TOC content is a valuable proxy for past primary productivity, whereas the solid phase Batot contents appear to be affected by other mechanisms and factors. Peaks of total barium content in the clay fraction and of Ba/Ca ratios in the planktonic foraminifera shells found during the Younger Dryas and the Heinrich 1 event are likely to result from increased meltwater influx into the northern North Atlantic. We suggest that Ba-enriched meltwater was transmitted by the eastern boundary current system from higher latitudes to the region of the Canary Islands. Total barium contents of the clay fraction (Batot,clay) and Ba/Ca in planktonic foraminifera shells seem to be reliable proxies for this discharge of meltwater.

Stable hydrogen isotopic composition (dD) and stable carbon isotopic composition (d13C) of sediment core GeoB9508-5 off Senegal

To reconstruct variability of the West African monsoon and associated vegetation changes on precessional and millennial time scales, we analyzed a marine sediment core from the continental slope off Senegal spanning the past 44,000 years (44 ka). We used the stable hydrogen isotopic composition (dD) of individual terrestrial plant wax n-alkanes as a proxy for past rainfall variability. The abundance and stable carbon isotopic composition (d13C) of the same compounds were analyzed to assess changes in vegetation composition (C3/C4 plants) and density. The dD record reveals two wet periods that coincide with local maximum summer insolation from 38 to 28 ka and 15 to 4 ka and that are separated by a less wet period during minimum summer insolation. Our data indicate that rainfall intensity during the rainy season throughout both wet humid periods was similar, whereas the length of the rainy season was presumably shorter during the last glacial than during the Holocene. Additional dry intervals are identified that coincide with North Atlantic Heinrich stadials and the Younger Dryas interval, indicating that the West African monsoon over tropical northwest Africa is linked to both insolation forcing and high-latitude climate variability. The d13C record indicates that vegetation of the western Sahel was consistently dominated by C4 plants during the past 44 ka, whereas C3-type vegetation increased during the Holocene. Moreover, we observe a gradual ending of the Holocene humid period together with unchanging ratio of C3 to C4 plants, indicating that an abrupt aridification due to vegetation feedbacks is not a general characteristic of this time interval.

Age models of northern North Atlantic sediment cores

Benthic foraminiferal stable isotope records from four high-resolution sediment cores, forming a depth transect between 1237 m and 2303 m on the South Iceland Rise, have been used to reconstruct intermediate and deep water paleoceanographic changes in the northern North Atlantic during the last 21 ka (spanning Termination I and the Holocene). Typically, a sampling resolution of ~100 years is attained. Deglacial core chronologies are accurately tied to North Greenland Ice Core Project (NGRIP) ice core records through the correlation of tephra layers and changes in the percent abundance of Neogloboquadrina pachyderma (sinistral) with transitions in NGRIP. The evolution from the glacial mode of circulation to the present regime is punctuated by two periods with low benthic d13C and d18O values, which do not lie on glacial or Holocene water mass mixing lines. These periods correlate with the late Younger Dryas/Early Holocene (11.5-12.2 ka) and Heinrich Stadial 1 (14.7-16.8 ka) during which time freshwater input and sea-ice formation led to brine rejection both locally and as an overflow exported from the Nordic seas into the northern North Atlantic, as earlier reported by Meland et al. (2008). The export of brine with low ?13C values from the Nordic seas complicates traditional interpretations of low d13C values during the deglaciation as incursions of southern sourced water, although the spatial extent of this brine is uncertain. The records also reveal that the onset of the Younger Dryas was accompanied by an abrupt and transient (~200-300 year duration) decrease in the ventilation of the northern North Atlantic. During the Holocene, Iceland-Scotland Overflow Water only reached its modern flow strength and/or depth over the South Iceland Rise by 7-8 ka, in parallel with surface ocean reorganizations and a cessation in deglacial meltwater input to the North Atlantic.

Sea surface temperature reconstruction for Mediterranean Sea samples

Alkenone unsaturation ratios and planktonic delta18O records from sediment cores of the Alboran, Ionian and Levantine basins in the Mediterranean Sea show pronounced variations in paleo-temperatures and -salinities of surface waters over the last 16,000 years. Average sea surface temperatures (SSTs) are low during the last glacial (averages prior to 13,000 years: 11-15°C), vary rapidly at the beginning of the Holocene, and increase to 17-18°C at all sites during S1 formation (dated between 9500 and 6600 calendar years). The modern temperature gradient (2-3°C) between the Mediterranean sub-basins is maintained during formation of sapropel S1 in the Eastern Mediterranean Sea. After S1, SSTs have remained uniform in the Alboran Sea at 18°C and have fluctuated around 20°C in the Ionian and Levantine Basin sites. The delta18O of planktonic foraminifer calcite decreases by 2 per mil from the late glacial to S1 sediments in the Ionian Basin and by 2.8 per mil in the Levantine Basin. In the Alboran Sea, the decrease is 1.7 per mil. Of the 2.8 per mil decrease in the Levantine Basin, the effect of global ice volume accounts for a maximum of 1.05 per mil and the temperature increase explains only a maximum of 1.3 per mil. The remainder is attributed to salinity changes. We use the temperature and salinity estimates to calculate seawater density changes. They indicate that a reversal of water mass circulation is not a likely explanation for increased carbon burial during S1 time. Instead, it appears that intermediate and deep water formation may have shifted to the Ionian Sea approximately 2000 years before onset of S1 deposition, because surface waters were as cold, but saltier than surface water in the Levantine Basin during the Younger Dryas. Sapropel S1 began to form at the same time, when a significant density decrease also occurred in the Ionian Sea.

Diatom, ice rafted debris and Neogloboquadrina pachyderma (sinistral) abundance in sediment core OCE326-GGC14

A high-resolution diatom census coupled with other proxy data from Laurentian Fan (LF) provides a detailed description of the last deglaciation, bringing new insight to that period by revealing directly the timing of sea-ice formation and melting. Cold events Heinrich Event 1 (H1) and the Younger Dryas (YD) were multiphase events. H1 (~16.8-15.7 cal kyr BP) was defined by a two-pulse release of icebergs promoting sea-ice formation. Melting of sea-ice after H1 corresponds to a cold and fresh anomaly that may have kept the Bølling colder than the Allerød. At ~13.6 cal kyr BP, a cooling trend culminated with sea-ice formation, marking the YD onset (~12.8 cal kyr BP). The decrease in sea-ice (~12.2 cal kyr BP) led to a YD second phase characterized by very cold winters. However, the contribution of warm water diatoms tends to increase at the same time and the YD gradual end (~11.6 cal kyr BP) contrasts with its abrupt end in Greenland ice cores. The YD cannot be regarded as an event triggered by a fresh water input through the Laurentian Channel since only one weak brief input nearly 1000 yrs after its onset is recorded. Very cold and cool conditions without ice mark the following Preboreal. A northward heat flux between 10.8 and 10.2 cal kyr BP was interrupted by the increased influence of coastal waters likely fed by inland melting. There was no further development of sea-ice or ice-drift then.