(Table T1) Scanning electron microscope (SEM) analyses of IODP Site 321-U1338

The late Miocene to early Pliocene carbonate-rich sediments recovered at Integrated Ocean Drilling Program (IODP) Site U1338 during the Expedition 320/321 Pacific Equatorial Age Transect (PEAT) program contain abundant calcareous nanno- and microfossils. Geochemical proxies from benthic and planktonic foraminiferal and coccolithophore calcite could be very useful at this location; however, good preservation of the calcite is crucial for the proxies to be robust. Here, we evaluate the preservation of specific benthic and planktonic foraminifer species and coccolithophores in fine fraction sediment at Site U1338 using backscattered electron (topography mode) scanning electron microscopy (BSE-TOPO SEM). Both investigated foraminiferal species, Cibicidoides mundulus and Globigerinoides sacculifer, have undergone some alteration. The C. mundulus show minor evidence for dissolution, and only some specimens show evidence of overgrowth. The Gs. sacculifer show definite signs of alteration and exhibit variable preservation, ranging from fair to poor; some specimens show minor overgrowth and internal recrystallization but retain original features such as pores, spine pits, and internal test-wall growth structure, whereas in other specimens the recrystallization and overgrowth disguise many of the original features. Secondary electron and BSE-TOPO SEM images show that coccolith calcite preservation is moderate or moderate to poor. Slight to moderate etching has removed central heterococcolith features, and a small amount of secondary overgrowth is also visible. Energy dispersive spectroscopy analyses indicate that the main sedimentary components of the fine fraction sediment are biogenic CaCO3 and SiO2, with some marine barite. Based on the investigations in this data report, geochemical analyses on benthic foraminifers are unlikely to be affected by preservation, although geochemical analyses on the planktonic foraminifers should be treated cautiously because of the fair to poor and highly variable preservation.

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.

Radiocarbon ages, diatom abundance and laminae description of sediment core MD03-2597

Laminated sediments are unique archives of palaeoenvironmental and palaeoceanographic conditions, recording changes on seasonal and interannual timescales. Diatom-rich laminated marine sediments are examined from Dumont d'Urville Trough, East Antarctic Margin, to determine changes in environmental conditions on the continental shelf from 1136 to 3122 cal. yr BP. Scanning electron microscope backscattered electron imagery (BSEI) and secondary electron imagery are used to analyse diatom assemblages from laminations and to determine interlamina relationships. Diatom observations are quantified with conventional assemblage counts. Laminae are primarily classified according to visually dominant species identified in BSEI and, secondarily, by terrigenous content. Nine lamina types are identified and are characterized by: Hyalochaete Chaetoceros spp. resting spores (CRS); CRS and Fragilariopsis spp.; Fragilariopsis spp.; Corethron pennatum and Rhizosolenia spp.; C. pennatum; Rhizosolenia spp.; mixed diatom assemblage; Stellarima microtrias resting spores (RS), Porosira glacialis RS and Coscinodiscus bouvet; and P. glacialis RS. Formation of each lamina type is controlled by seasonal changes in sea ice cover, nutrient levels and water column stability. Quantitative diatom assemblage analysis revealed that each lamina type is dominated by CRS and Fragilariopsis sea ice taxa, indicating that sea ice cover was extensive and persistent in the late Holocene. However the lamina types indicate that the sea ice regime was not consistent throughout this period, notably that a relatively warmer period, ~3100 to 2500 cal. yr BP, was followed by cooling which resulted in an increase in year round sea ice by ~1100 cal. yr BP.

Late Neogene sediment composition and accumulation rates of ODP Hole 120-751A

Through scanning electron microscope analysis of sediment microfabric, we have evaluated variations in high-resolution shipboard physical properties (index properties and shear strength), sediment components (smear slide determinations), and shore-based calcium carbonate and biogenic silica data from Site 751 (Kerguelen Plateau). The stratigraphic section at this site records a change in biogenic ooze composition from predominantly calcareous (nannofossil) to siliceous (diatom) ooze from ~23 Ma to the present, reflecting expansion of Antarctic water masses during the late Neogene. The profound change in physical properties and sediment character at 40.1 mbsf (~5-6 Ma) evidently records the northward movement of the Polar Front and a change in absolute accumulation rates of sediment at this site. Trends in geotechnical properties with depth at Site 751 allowed us to subdivide the sedimentary column into a number of geotechnical units that reflect changes in depositional and postdepositional processes with time. Geotechnical properties are sensitive to changing sedimentary inputs of primarily siliceous and calcareous microfossils. This allows us to study the physical nature of biostratigraphically-identified hiatuses and variations in environmental conditions linked to the migration of the Polar Front across this region. The analysis of geotechnical properties permits a more detailed division of the sedimentary column than is possible from shipboard lithologic descriptions alone. Our study of the sedimentary microfabric indicates that randomly oriented, elongate pennate diatom valves compose the sediments with highest porosity and water content values, and the lowest density values (wet bulk, dry bulk, and grain density). Conversely, sediments composed of nannofossils and disassociated nannofossil crystallites and little or no siliceous remains have the lowest porosity and water content values, and the highest density values. Samples of mixed siliceous/calcareous composition have intermediate physical property values, but these vary according to the nature of the sedimentary matrix and the state of preservation of individual skeletal elements.

Calcareous dinoflagellates in Cretaceous to Recent sediments of DSDP Hole 39-356

Calcareous dinoflagellates often dominate the dinoflagellate cyst assemblage in Cretaceous to Recent oceanic sediments. However, their distribution in Paleogene sediments has scarcely been studied. The investigation of samples from DSDP Site 356 for their calcareous dinoflagellate content revealed 35 mainly long-ranging taxa. The associations and characteristic wall types (pithonelloid, oblique, radial, tangential) fluctuate quantitatively and qualitatively in distinct stratigraphic patterns. Significant shifts, primarily at the K/T boundary and the Paleocene/Eocene boundary, reflect changes in environmental conditions. Certain dinoflagellates forming calcareous cysts, such as Operculodinella operculata, were well adapted to the relatively rapid change of environmental conditions at the K/T boundary, thus blooming to dominate the carbonate flux to the ocean floor. In contrast to the stable Paleocene associations, Eocene calcareous dinoflagellates show fluctuations in relative abundances. These fluctuations can possibly be attributed to redeposition related to increased seaward transport of specimens, due to strengthened western boundary currents. The flora includes two new genera, one new species, and two new forms: Retesphaera diadema Hildebrand-Habel, Willems et Versteegh, gen. et. sp. nov., Cervisiella saxea (Stradner, 1961) Hildebrand-Habel, Willems et Versteegh, gen. et comb. nov., Sphaerodinella? tuberosa forma elongata Hildebrand-Habel, Willems et Versteegh, comb. et forma nov., Sphaerodinella? tuberosa forma variospinosa Hildebrand-Habel, Willems et Versteegh, comb. et forma nov. Three new combinations are proposed: Cervisiella saxea (Stradner, 1961) Hildebrand-Habel, Willems et Versteegh, gen. et comb. nov., Operculodinella operculata (Bramlette et Martini, 1964) Hildebrand-Habel, Willems et Versteegh, comb. nov., and Sphaerodinella? tuberosa (Kamptner, 1963) Hildebrand-Habel, Willems et Versteegh, comb. nov. The genus Operculodinella Kienel, 1994 is emended.

Sample locations, CTD data, mean spring and annual temperatures and salinities from World Ocean Atlas (WOA, 2001), and ICP-OES Mg/Ca data

Due to its strong gradient in salinity and small temperature gradient the Mediterranean provides an ideal setting to study the impact of salinity on the incorporation of Mg into foraminiferal tests. We have investigated tests of Globorotalia inflata and Globigerina bulloides in plankton tow and core top samples from the Western Mediterranean using ICP-OES for bulk analyses and LA-ICP-MS for analyses of individual chambers in single specimens. Mg/Ca observed in G. inflata are consistent with existing calibrations, whereas G. bulloides had significantly higher Mg/Ca than predicted, particularly in core top samples from the easterly stations. Scanning Electron Microscopy and Laser Ablation ICP-MS revealed secondary overgrowths on some tests, which could explain the observed high core top Mg/Ca. We suggest that the Mediterranean intermediate and deep water supersaturated with respect to calcite cause these overgrowths and therefore increased bulk Mg/Ca. However, the different species are influenced by diagenesis to different degrees probably due to different test morphologies. Our results provide new perspectives on reported anomalously high Mg/Ca in sedimentary foraminifera and the applicability of the Mg/Ca paleothermometry in high salinity settings, by showing that (1) part of the signal is generated by precipitation of inorganic calcite on the foraminifer test due to increased calcite saturation state of the water and (2) species with high surface-to-volume shell surfaces are potentially more affected by secondary Mg-rich calcite encrustation.

The distributions, C- and O-isotopic compositions, and frequency of giant-ooids

Early Triassic oceans were characterized by deposition of a number of "anachronistic facies", including microbialites, seafloor carbonate cement fans, and giant ooids. Giant ooids were particularly prevalent in Lower Triassic sections across South China and exhibit unusual features that may provide insights into marine environmental conditions following the end-Permian mass extinction. The section at Moyang (Guizhou Province) contains abundant giant ooids ranging in size between 2 and 6 mm (maximum 12 mm) and exhibiting various cortical structures, including regular, deformed, compound, regenerated and "domed". Preservation of ooid cortical structure is generally good as indicated by petrographic observations, and trace element and carbon isotope analyses suggest that diagenesis occurred in a closed diagenetic system. All ooids exhibit fine concentric laminae, frequently alternating between light-colored coarsely crystalline and dark-colored finely crystalline layers probably reflecting variation in organic content or original mineralogy. Under scanning electron microscope, biomineralized filaments or biofilms and tiny carbonate fluorapatite (CFA) crystals are commonly found in the finely crystalline layers. We infer that the precipitation of CFA was related to adsorption of P via microbial activity on the surfaces of ooids following episodic incursions of deep waters rich in carbon dioxide, hydrogen sulfide and phosphate into shallow-marine environments. Giant ooid precipitation may have been promoted in shallow ramp settings during these events by increased watermass agitation and supersaturation with respect to calcium carbonate, as well as reduced carbonate removal rates through biotic skeletal formation. Spatio-temporal distribution data reveal that giant ooids were widespread in the Tethyan region during the Early Triassic, and that they were most abundant immediately after the end-Permian crisis and disappeared gradually as metazoans repopulated marine environments.

Microsedimentological characterization as indicators of sedimentary processes and climate changes during Lateglacial at Laguna Potrok Aike, Santa Cruz, Argentina

Palaeoclimatic and paleoenvironmental high latitude records in the Southern Hemisphere are scarce compared to the northern counterpart. However, understanding global evolution of environmental systems during sudden climate changes is inseparable from an equivalent knowledge of both Hemispheres. In this context, a high-resolution study of lacustrine sediments from Laguna Potrok Aike, Santa Cruz province, Patagonia, Argentina, was conducted for the Lateglacial period using concurrent X-Ray Fluorescence (XRF) and Scanning electron microscope analyses. Peaks of Ca/Si and Mn, and occurrences of the green alga Phacotus lenticularis have been interpreted as variations in ventilation of the water column from 13.6 to 11.1 ka cal. BP. During this interval, mild climate conditions during the Younger Dryas are characterized by relatively weak westerlies favouring the formation of a stratified water body as indicated by preserved manganese and Ca/Si peaks and high Total Organic Carbon (TOC) values. In this environment, water in the epilimnion can reach sufficiently high temperature to allow P. lenticularis to grow. Colder conditions are marked by peaks in Ca without P. lenticularis and occur during the Antarctic Cold Reversal (ACR). In this Lateglacial interval, micropumices were also detected in large amount. Image analysis of thin sections allowed the counting and size measurement of detrital particles and micropumices separately. Micropumices significantly influence the iron and titanium content, hence preventing to use them as proxies of detrital input in this interval.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.