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.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Geochemistry of Lesser Antilles lavas

We present new U-series disequilibrium and radiogenic isotope data for 7 mafic lavas from the Lesser Antilles arc. These are combined with published data in an internally consistent model that quantitatively estimates the amount of sediment and fluid added to the source of the Lesser Antilles arc system. Some lavas form an array consistent with bulk sediment addition (0.2-2%) whereas others appear to require addition of 0.4-2% sediment melt, particularly in the south of the arc. Evidence for both bulk sediment and sediment melt addition can be found within both the northern and central sections of the arc suggesting a thermal structure whereby the upper portions of the subducted sediment pile lie close to their solidus beneath much of the arc. Addition of up to 5% fluid derived from altered oceanic crust to these sediment enriched mantle wedge source regions can simulate the majority of the lavas on a plot of 207Pb/204Pb versus Ce/Pb. By taking into account the range in calculated wedge compositions and allowing for some mobility of Th in the fluid, the same model can also account for much of the observed range of U-Th-Ra disequilibria, especially if the eclogitic residue contains trace amounts of rutile. The implication of this more complex model is that the time scales for fluid addition and differentiation could be significantly shorter than those estimated in some previous studies.

A deep-sea coral record of the North Atlantic

Our record of Younger Dryas intermediate-depth seawater D14C from North Atlantic deep-sea corals supports a link between abrupt climate change and intermediate ocean variability. Our data show that northern source intermediate water (~1700 m) was partially replaced by 14C-depleted southern source water at the onset of the event, consistent with a reduction in the rate of North Atlantic Deep Water formation. This transition requires the existence of large, mobile gradients of D14C in the ocean during the Younger Dryas. The D14C water column profile from Keigwin (2004) provides direct evidence for the presence of one such gradient at the beginning of the Younger Dryas (~12.9 ka), with a 100 per mil offset between shallow (<~2400 m) and deep water. Our early Younger Dryas data are consistent with this profile and also show a D14C inversion, with 35 per mil more enriched water at ~2400 m than at ~1700 m. This feature is probably the result of mixing between relatively well 14C ventilated northern source water and more poorly 14C ventilated southern source intermediate water, which is slightly shallower. Over the rest of the Younger Dryas our intermediate water/deepwater coral D14C data gradually increase, while the atmosphere D14C drops. For a very brief interval at ~12.0 ka and at the end of the Younger Dryas (11.5 ka), intermediate water D14C (~1200 m) approached atmospheric D14C. These enriched D14C results suggest an enhanced initial D14C content of the water and demonstrate the presence of large lateral D14C gradients in the intermediate/deep ocean in addition to the sharp vertical shift at ~2500 m. The transient D14C enrichment at ~12.0 ka occurred in the middle of the Younger Dryas and demonstrates that there is at least one time when the intermediate/deep ocean underwent dramatic change but with much smaller effects in other paleoclimatic records.

Coral Sr/Ca records from Bonaire Holocene corals

Proxy reconstructions of tropical Atlantic sea surface temperature (SST) that extend beyond the period of instrumental observations have primarily focused on centennial to millennial variability rather than on seasonal to multidecadal variability. Here we present monthly-resolved records of Sr/Ca (a proxy of SST) from fossil annually-banded Diploria strigosa corals from Bonaire (southern Caribbean Sea). The individual corals provide time-windows of up to 68 years length, and the total number of 295 years of record allows for assessing the natural range of seasonal to multidecadal SST variability in the western tropical Atlantic during snapshots of the mid- to late Holocene. Comparable to modern climate, the coral Sr/Ca records reveal that mid- to late Holocene SST was characterised by clear seasonal cycles, persistent quasi-biennial and prominent interannual as well as inter- to multidecadal-scale variability. However, the magnitude of SST variations on these timescales has varied over the last 6.2 ka. The coral records show increased seasonality during the mid-Holocene consistent with climate model simulations indicating that southern Caribbean SST seasonality is induced by insolation changes on orbital timescales, whereas internal dynamics of the climate system play an important role on shorter timescales. Interannual SST variability is linked to ocean-atmosphere interactions of Atlantic and Pacific origin. Pronounced interannual variability in the western tropical Atlantic is indicated by a 2.35 ka coral, possibly related to a strengthening of the variability of the El Niño/Southern Oscillation throughout the Holocene. Prominent inter- to multidecadal SST variability is evident in the coral records and slightly more pronounced in the mid-Holocene. We finally argue that our coral data provide a target for studying Holocene climate variability on seasonal and interannual to multidecadal timescales, when using further numerical models and high-resolution proxy data.