(Table 2) Uranium series results of Villars Cave stalagmite Vil-stm14

We present a new high resolution speleothem stable isotope record from the Villars Cave (SW-France) that covers part of marine isotope stage (MIS) 3. The Vil14 stalagmite grew between ~52 and 29 ka. The d13C profile is used as a palaeoclimate proxy and clearly shows the interstadial substages 13, 12 and 11. The new results complement and corroborate previously published stalagmite records Vil9 and Vil27 from the same site. The Vil14 stalagmite chronology is based on 12 Th-U dating by MC-ICP-MS and 3 by TIMS. A correction for detrital contamination was done using the 230Th/232Th activity ratio measured on clay collected in Villars Cave. The Vil14 results reveal that the onset of Dansgaard-Oeschger (DO) events 13 and 12 occurred at ~49.8 ka and ~47.8 ka, respectively. Within uncertainties, this is coherent with the latest NorthGRIP time scale (GICC05-60 ka) and with speleothem records from Central Alps. Our data show an abrupt d13C increase at the end of DO events 14 to 12 which coincides with a petrographical discontinuity probably due to a rapid cooling. As observed for Vil9 and Vil27, Vil14 growth significantly slowed down after ~ 42 ka and finally stopped ~ 29 ka ago where the d13C increase suggests a strong climate deterioration that coincides with both North Atlantic sea level and sea surface temperature drop.

Uranium-Thorium dating and sea surface temperatures from corals from Hainan Island, South China Sea

Three mid-Holocene sea surface temperature (SST) records spanning more than 30 years were reconstructed for the northern South China Sea using Sr/Ca ratios in Porites corals. The results indicate warmer than present climates between circa 6100 yr B.P. and circa 6500 yr B.P. with the mid-Holocene average minimum monthly winter SSTs, the average maximum monthly summer SSTs, and the average annual SSTs being about 0.5°-1.4°C, 0°-2.0°C, and 0.2°-1.5°C higher, respectively, than they were during 1970-1994. Summer SSTs decrease from circa 6500 yr B.P. to circa 6100 yr B.P. with a minimum centered at circa 6300 yr B.P. The higher average summer SSTs are consistent with a stronger summer monsoon during the mid-Holocene, and the decreasing trend indicates a secular decrease of summer monsoon strength, which reflects the change in summer insolation in the Northern Hemisphere. El Niño-Southern Oscillation (ENSO) cycles were apparent in both the mid-Holocene coral and modern instrumental records. However, the ENSO variability in the mid-Holocene SSTs was weaker than that in the modern record, and the SST record with the highest summer temperatures from circa 6460 yr B.P. to 6496 yr B.P. shows no robust ENSO cycle. This agrees with other studies that indicate that stronger summer monsoon circulation may have been associated with suppressed ENSO variability during the mid-Holocene.

Benthic foraminifera and sea level analyses from IODP Hole 310-M0005D

The course of sea-level fluctuations during Termination II (TII; the penultimate deglaciation), which is critical for understanding ice-sheet dynamics and suborbital climate variability, has yet to be established. This is partly because most shallow-water sequences encompassing TII were eroded during sea-level lowstands of the last glacial period or were deposited below the present sea level. Here we report a new sequence recording sea-level changes during TII in the Pleistocene sequence at Hole M0005D (water depth: 59.63 m below sea level [mbsl]) off Tahiti, French Polynesia, which was drilled during Integrated Ocean Drilling Program Expedition 310. Lithofacies variations and stratigraphic changes in the taxonomic composition, preservation states, and intraspecific test morphology of large benthic foraminifers indicate a deepening-upward sequence in the interval from Core 310-M0005D-26R (core depth: 134 mbsl) through -16R (core depth: 106 mbsl). Reconstruction of relative sea levels, based on paleodepth estimations using large benthic foraminifers, indicated a rise in sea level of about 90 m during this interval, suggesting its correlation with one of the terminations. Assuming that this rise in sea level corresponds to that during TII, after correcting for subsidence since the time of deposition, a highstand sea-level position would be 2 ± 15 m above present sea level (masl), which is generally consistent with highstand sea-level positions in MIS 5e (4 ± 2 masl). If this rise in sea level corresponds to that during older terminations, the subsidence-corrected highstand sea-level positions (30 ± 15 masl for Termination III and 54 ± 15 masl for Termination IV) are not consistent with reported ranges of interglacial sea-level highstands (-18 to 15 masl). Therefore, the studied interval likely records the rise in sea level and associated environmental changes during TII. In particular, the intervening cored materials between the two episodes of sea-level rise found in the studied interval might record the sea-level reversal event during TII. This conclusion is consistent with U/Th ages of around 133 ka, which were obtained from slightly diagenetically altered (i.e., < 1% calcite) in situ corals in the studied interval (Core 310-M0005D-20R [core depth: 118 mbsl]). This study also suggests that our inverse approach to correlate a stratigraphic interval with an approximate time frame could be useful as an independent check on the accuracy of uranium-series dating, which has been applied extensively to fossil corals in late Quaternary sea-level studies.

U-series ages from calcitic cold-water corals from the Amundsen Sea

Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) and which to date have not been investigated geochemically. The geochronological results are set in context with solution and laser ablation-based element/Ca ratios (Li, B, Mg, Mn, Sr, Ba, U, Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water D14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial d234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral d234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uranium mobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water D14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

(Table A1) Uranium and Thorium determination from IODP Site 310-M0007B

The Integrated Ocean Drilling Program (IODP) Expedition 310 recovered drill cores from the drowned reefs around the island of Tahiti (17°40'S, 149°30'W), many of which contained samples of massive corals from the genus Porites. Herein we report on one well-preserved fossil coral sample: a 13.6 cm long Porites sp. dated by uranium series techniques at 9523 ± 33 years. Monthly delta18O and Sr/Ca determinations reveal nine clear and robust annual cycles. Coral delta18O and Sr/Ca determinations estimate a mean temperature of ca. 24.3°C (ca. 3.2°C colder than modern) for Tahiti at 9.5 ka; however, this estimate is viewed with caution since potential sources of cold bias in coral geochemistry remain to be resolved. The interannual variability in coral delta18O is similar between the 9.5 ka coral record and a modern record from nearby Moorea. The seasonal cycle in coral Sr/Ca is approximately the same or greater in the 9.5 ka coral record than in modern coral records from Tahiti. Paired analysis of coral delta18O and Sr/Ca indicates cold/wet (warm/dry) interannual anomalies, opposite from those observed in the modern instrumental record.

Uranium radionuclides and organic biomarkers in sediment core RC27-42

Uranium series radionuclides and organic biomarkers, which represent major groups of planktonic organisms, were measured in western Arabian Sea sediments that span the past 28 ka. Variability in the past strength of the southwest and northeast monsoons and its influence on primary productivity, sea surface temperature (SST), and planktonic community structure were investigated. The average alkenone-derived SST for the last glacial period was ~3°C lower than that measured for the Holocene. Prior to the deglacial, the lowest SSTs coincide with the highest measured fluxes of organic biomarkers, which represent primarily a planktonic suite of diatoms, coccolithophorids, dinoflagellates, and zooplankton. We propose that intensification of winter northeast monsoon winds during the last glacial period resulted in deep convective mixing, cold SSTs and enhanced primary productivity. In contrast, postdeglacial (<17 ka) SSTs are warmer during times in which biomarker fluxes are high. Associated with this transition is a planktonic community structure change, in which the ratio of the average cumulative flux of diatom biomarkers to the cumulative flux of coccolithophorid biomarkers is twice as high during the deglacial and Holocene than the average ratio during the last glacial period. We suggest that this temporal transition represents a shift from a winter northeast monsoon-dominated (pre-17 ka) to a summer southwest monsoon-dominated (post-17 ka) wind system.

(Table S1) Uranium and Thorium isotopes and U/Th ages of IODP Exp310 cores from offshore Tahiti

The timing of sea-level change provides important constraints on the mechanisms driving Earth's climate between glacial and interglacial states. Fossil corals constrain the timing of past sea level by their suitability for dating and their growth position close to sea level. The coral-derived age for the last deglaciation is consistent with climate change forced by Northern Hemisphere summer insolation (NHI), but the timing of the penultimate deglaciation is more controversial. We found, by means of uranium/thorium dating of fossil corals, that sea level during the penultimate deglaciation had risen to ~85 meters below the present sea level by 137,000 years ago, and that it fluctuated on a millennial time scale during deglaciation. This indicates that the penultimate deglaciation occurred earlier with respect to NHI than the last deglacial, beginning when NHI was at a minimum.

Cape Lookout cold-water coral area, coral ages and environmental parameters for the last glacial cycle

Climatic and oceanographic changes, as occurring at a glacial-interglacial scale, may alter the environmental conditions needed for the development of prolific cold-water coral reefs and mounds. Studies constraining the temporal distribution of cold-water corals in the NE Atlantic suggested the cyclic changes of the Atlantic Meridional Overturning Circulation as the main driver for the development and dispersal of cold-water coral ecosystems. However, conclusions were hindered by lack of data from the NW Atlantic. Aiming to overcome this lack of data, the temporal occurrence of cold-water corals in the Cape Lookout area along the southeastern US margin was explored by U-series dating. Furthermore, the local influence of the regional water masses, namely the Gulf Stream, on cold-water coral proliferation and occurrence since the Last Glacial Maximum was examined. Results suggest that the occurrence of cold-water corals in the Cape Lookout area is restricted to interglacial periods, with corals being present during the last ~7 kyr and also during the Eemian (~125 ka). The reconstructed local environmental conditions suggest an offshore displacement of the Gulf Stream and increased influence from the Mid-Atlantic Bight shelf waters during the last glacial period. During the deglacial sea level rise, the Gulf Stream moved coastward providing present-day-like conditions to the surface waters. Nevertheless, present-day conditions at the ocean sea floor were not established before 7.5 cal ka BP once the ultimate demise of the Laurentide ice-sheet caused the final sea level rise and the displacement of the Gulf Stream to its present location. Occasional presence of the Gulf Stream over the site during the Mid- to Late Holocene coincides with enhanced bottom current strength and a slightly higher bottom water temperature, which are environmental conditions that are favorable for cold-water coral growth.

Th-U ages of a stalagmite from the Kleegruben Cave (Table 1)

A mass-spectrometric uranium-series dated stalagmite from the Central Alps of Austria provides unprecedented new insights into high-altitude climate change during the peak of isotope stage 3. The stalagmite formed continuously between 57 and 46 kyr before present. A series of 'Hendy tests' demonstrates that the outer parts of the sample show a progressive increase of both stable C and O isotope values. No such covariant increase was detected within the axial zone. This in conjunction with other observations suggests that the continuous stable oxygen isotope profile obtained from the axial zone of the stalagmite largely reflects the unaltered isotopic composition of the cave drip water. The delta18O record shows events of high delta18O values that correlate remarkably with Interstadials 15 (a and b), 14 and 12 identified in the Greenland ice cores. Interstadial 15b started rapidly at 55.6 kyr and lasted ~300 yr only, Interstadial 15a peaked 54.9 kyr ago and was even of shorter duration (~100 yr), and Interstadial 14 commenced 54.2 kyr ago and lasted ~3000 yr. This stalagmite thus represents one of the first terrestrial archives outside the high latitudes which record precisely dated Dansgaard-Oeschger (D/O) events during isotope stage 3. Provided that rapid D/O warmings occurred synchronously in Greenland and the European Alps, the new data provide an independent tool to improve the GRIP and GISP2 chronologies.