(Table 3) Run conditions and phase relations and proportions during cooling rate experiments on ODP Interval 163-989B-10R-7,55-59

Equilibrium melting and controlled cooling experiments were undertaken to constrain the crystallization and cooling histories of tholeiitic basalts recovered by the Ocean Drilling Program drilling of Site 989 on the Southeast Greenland continental margin. Isothermal experiments conducted at 1 atm. and at the fayalite-magnetite-quartz buffer using lava sample Section 163-989B-10R-7 yielded the equilibrium appearance sequence with decreasing temperature: olivine at 1184 ± 2ºC; plagioclase at 1177ºC ± 5ºC; augite at 1167 ± 5ºC; and pigeonite at 1113 ± 12ºC. In controlled cooling experiments using the same starting composition and cooling rates between 10ºC/hr and 2000ºC/hr, we find a significant temperature delay in the crystallization of olivine, plagioclase, and augite (relative to the equilibrium appearance temperature); pigeonite does not form under any dynamic crystallization conditions. Olivine exhibits the largest suppression in appearance temperature (e.g., 30º for 10ºC/hr and >190º at 100ºC/hr), while plagioclase shows the smallest (~10ºC at 10ºC/hr; 30ºC at 100ºC/hr, and ~80ºC at 1000ºC/hr). These results are in marked contrast to those obtained on lunar basalts, which generally show a large suppression of plagioclase crystallization and modest suppression of olivine crystallization with an increased cooling rate. The results we report agree well with the petrography of lavas recovered from Site 989. Furthermore, the textural analysis of run products, representing a large range of cooling rates and quench temperatures (1150ºC to 1000ºC), provide a framework for evaluating cooling conditions necessary for glass formation, rates of plagioclase growth, and kinetic factors governing plagioclase growth morphology. Specifically, we use these insights to interpret the textural and mineralogical features of the unusual compound flow recovered at Site 989. We concluded from the analysis that this flow most likely records multiple breakouts from a distal tube at an abrupt break in slope, possibly a fault scarp, resulting in the formation of a lava fan delta. This interpretation implies that normal faulting of the oldest lava sequences (lower and, possibly, middle series) preceded eruption of Site 989 lavas.

Cretaceous stable isotopic record and sea surface temperture estimation for ODP Site 207-1259

The Turonian (93.5 to 89.3 million years ago) was one of the warmest periods of the Phanerozoic eon, with tropical sea surface temperatures over 35°C. High-amplitude sea-level changes and positive d18O excursions in marine limestones suggest that glaciation events may have punctuated this episode of extreme warmth. New d18O data from the tropical Atlantic show synchronous shifts ~91.2 million years ago for both the surface and deep ocean that are consistent with an approximately 200,000-year period of glaciation, with ice sheets of about half the size of the modern Antarctic ice cap. Even the prevailing supergreenhouse climate was not a barrier to the formation of large ice sheets, calling into question the common assumption that the poles were always ice-free during past periods of intense global warming.

Sea surface temperature estimation for the last 70 ka from IODP Site 306-U1313

During the six Heinrich Events of the last 70 ka episodic calving from the circum-Atlantic ice sheets released large numbers of icebergs into the North Atlantic. These icebergs and associated melt-water flux are hypothesized to have led to a shutdown of Atlantic Meridional Overturning Circulation (AMOC) and severe cooling in large parts of the Northern Hemisphere. However, due to the limited availability of high-resolution records the magnitude sea surface temperature (SST) changes related to the impact of Heinrich Events on the mid-latitude North Atlantic is poorly constrained. Here we present a record of UK37'-based SSTs derived from sediments of Integrated Ocean Drilling Project (IODP) Site U1313, located at the southern end of the ice-rafted debris (IRD)-belt in the mid-latitude North Atlantic (41°N). We demonstrate that all six Heinrich Events are associated with a rapid warming of surface waters by 2 to 4°C in a few thousand years. The presence of IRD leaves no doubt about the simultaneous timing and correlation between rapid surface water warming and Heinrich Events. We argue that this warming in the mid-latitude North Atlantic is related to a northward expansion of the subtropical gyre during Heinrich Events. As a wide-range of studies demonstrated that in the central IRD-belt Heinrich Events are associated with low SSTs, these results thus identify an anti-phased (seesaw) pattern in SSTs during Heinrich Events between the mid-latitude (warm) and northern North Atlantic (cold). This highlights the complex response of surface water characteristics in the North Atlantic to Heinrich Events that is poorly reproduced by fresh water hosing experiments and challenges the widely accepted view that within the IRD-belt of the North Atlantic Heinrich Events coincide with periods of low SSTs.

Summary of phase compositions of experimental silicate melt, un-normalised analyses

The solubility of Re and Au in haplobasaltic melt has been investigated at 1673-2573 K, 0.1 MPa-2 GPa and IW-1 to +2.5, in both carbon-saturated and carbon-free systems. Results extend the existing, low pressure and temperature, dataset to more accurately predict the results of metal-silicate equilibrium at the base of a terrestrial magma ocean. Solubilities in run-product glasses were measured by laser ablation ICP-MS, which allows for the explicit assessment of contamination by metal inclusions. The Re and Au content of demonstrably contaminant-free glasses increases with temperature, and shows variation with oxygen fugacity (fO2) similar to previous results, although lower valence states for Re (1+, 2+) are suggested by the data. At 2 GPa, and Delta IW of +1.75 to +2, the metal-silicate partition coefficient for Re (DMet/Sil) is defined by the relation LogD[met/sil][Re] = 0.50(±0.022)*10**4/T(K)+3.73(±0.095) For metal-silicate equilibrium to endow Earth's mantle with the observed time-integrated chondritic Re/Os, (and hence 187Os/188Os), DMet/Sil for both elements must converge to a common value. Combined with previously measured DMet/Sil for Os, the estimated temperature at which this convergence occurs is 4500 (±900) K. At this temperature, however, the Re and Os content of the equilibrated silicate is ~100-fold too low to explain mantle abundances. In the same experiments, much lower Dmet/sil values have been determined for Au, and require the metal-silicate equilibration temperature to be <3200 K, as hotter conditions result in an excess of Au in the mantle. Thus, the large disparity in partitioning between Re or Os, and Au at core-forming temperatures argues against their mantle concentrations set solely by metal-silicate equilibrium at the base of a terrestrial magma ocean.

Sea surface temperature estimation for MIS 16 of IODP Site 306-U1313

Hudson Strait (HS) Heinrich Events, ice-rafting events in the North Atlantic originating from the Laurentide ice sheet (LIS), are among the most dramatic examples of millennial-scale climate variability and have a large influence on global climate. However, it is debated as to whether the occurrence of HS Heinrich Events in the (eastern) North Atlantic in the geological record depends on greater ice discharge, or simply from the longer survival of icebergs in cold waters. Using sediments from Integrated Ocean Drilling Program (IODP) Site U1313 in the North Atlantic spanning the period between 960 and 320 ka, we show that sea surface temperatures (SSTs) did not control the first occurrence of HS Heinrich(-like) Events in the sedimentary record. Using mineralogy and organic geochemistry to determine the characteristics of ice-rafting debris (IRD), we detect the first HS Heinrich(-like) Event in our record around 643 ka (Marine Isotope Stage (MIS) 16), which is similar as previously reported for Site U1308. However, the accompanying high-resolution alkenone-based SST record demonstrates that the first HS Heinrich(-like) Event did not coincide with low SSTs. Thus, the HS Heinrich(-like) Events do indicate enhanced ice discharge from the LIS at the end of the Mid-Pleistocene Transition, not simply the survivability of icebergs due to cold conditions in the North Atlantic.

Sea surface temperature estimation of the South Tasman Rise

The Subtropical Front (STF) marking the northern boundary of the Southern Ocean has a steep gradient in sea surface temperature (SST) of approximately 4°C over 0.5° of latitude. Presently, in the region south of Tasmania, the STF lies nominally at 47°S in the summer and 45°S in the winter. We present here SST reconstructions in a latitudinal transect of cores across the South Tasman Rise, southeast of Australia, during the late Quaternary. SST reconstructions are based on two paleotemperature proxies, alkenones and faunal assemblages, which are used to assess past changes in SST in spring and summer. The north-south alignment in core locations allows reconstruction of movement of the STF over the last 100 ka. Surface water temperatures during the last glaciation in this region were ~4°C colder than today. Additional temperature changes greater in magnitude than 4°C seen in individual cores can be attributed to changes in the water mass overlying the core site caused by the movement of the front across that location. During the penultimate interglacial, SST was ~2°C warmer and the STF was largely positioned south of 47°S. Movement of the STF to the north occurred during cool climate periods such as the last marine isotope stages 3 and 4. In the last glaciation, the front was at its farthest north position, becoming pinned against the Tasmanian landmass. It moved south by 4° latitude to 47°S in summer during the deglaciation but remained north of 45°S in spring throughout the early deglaciation. After 11 ka B.P. inferred invigoration of the East Australia Current appears to have pushed the STF seasonally south of the East Tasman Plateau, until after 6 ka B.P. when it achieved its present configuration.

Temperature and CO2 estimation for the Middle Eocene section of ODP Hole 189-1172A

The long-term warmth of the Eocene (~56 to 34 million years ago) is commonly associated with elevated partial pressure of atmospheric carbon dioxide (pCO2). However, a direct relationship between the two has not been established for short-term climate perturbations. We reconstructed changes in both pCO2 and temperature over an episode of transient global warming called the Middle Eocene Climatic Optimum (MECO; ~40 million years ago). Organic molecular paleothermometry indicates a warming of southwest Pacific sea surface temperatures (SSTs) by 3° to 6°C. Reconstructions of pCO2 indicate a concomitant increase by a factor of 2 to 3. The marked consistency between SST and pCO2 trends during the MECO suggests that elevated pCO2 played a major role in global warming during the MECO.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Chemistry of fluid inclusions in rock samples from Dronning Maud Land

Dense, CO2-rich fluid inclusions hosted by plagioclases, An45 to An54, of the O.-v.-Gruber- Anorthosite body, central Dronning Maud Land, East Antarctica, contain varying amounts of small calcite, paragonite and pyrophyllite crystals detected by Raman microspectroscopy. These crystals are reaction products that have formed during cooling of the host and the original CO2-rich H2O-bearing enclosed fluid. Variable amounts of these reaction products illustrates that the reaction did not take place uniformly in all fluid inclusions, possibly due to differences in kinetics as caused by differences in shape and size, or due to compositional variation in the originally trapped fluid. The reaction albite + 2anorthite + 2H2O + 2CO2 = pyrophyllite + paragonite + 2calcite was thermodynamically modelled with consideration of different original fluid compositions. Although free H2O is not detectable in most fluid inclusions, the occurrence of OH-bearing sheet silicates indicates that the original fluid was not pure CO2, but contained significant amounts of H2O. Compared to an actual fluid inclusion it is obvious, that volume estimations of solid phases can be used as a starting point to reverse the retrograde reaction and recalculate the compositional and volumetrical properties of the original fluid. Isochores for an unmodified inclusion can thus be reconstructed, leading to a more realistic estimation of P-T conditions during earlier metamorphic stages or fluid capturing.

Estimation of cooling of lavas from Serocki volcano

A dynamic crystallization study was undertaken to provide a framework for linking the textural variations observed in the Hole 648B lavas with the size and morphology of cooling units inferred from drilling and submersible observation. The textures produced in cooling rate experiments carried out using a Serocki lava (ALV-1690-20) are comparable to the groundmass textural characteristics of lavas from Serocki volcano. The results of the dynamic crystallization study provide a quantitative link between texture, cooling rate, and eruption temperature. The maximum half-width of cooling units estimated from textural characteristics is on the order of 3 m, a value consistent with constraints from drilling and submersible observation. Textural characteristics indicate that the temperature from which cooling began was slightly above the liquidus. The relation between cooling rate and texture are also tested on a drill core sample of basalt of similar composition from a 9-m-thick flow in DSDP Hole 396B.