(Appendix) Oxygen isotope record and carbonate mineralogy of the top part of ODP Hole 101-633A

Hole 633A was drilled in the southern part of Exuma Sound on the toe-of-slope of the southeastern part of Great Bahama Bank during ODP Leg 101. The top 55 m, collected as a suite of six approximately 9.5-m-long hydraulic piston cores, represents a Pliocene-Pleistocene sequence of periplatform carbonate ooze, a mixture of pelagic calcite (foraminifer and coccolith tests), some pelagic aragonite (pteropod tests), and bank-derived fine aragonite and magnesian calcite. A 1.6-m.y.-long hiatus was identified at 43.75 mbsf using calcareous nannofossil biostratigraphy and magnetostratigraphy. The 43.75-m-thick periplatform sequence above the hiatus is a complete late Pliocene-Quaternary record of the past 2.15 m.y. The d18O curve, primarily based on Globigerinoides sacculifera, clearly displays high-frequency/low-amplitude cycles during the early Pleistocene and low-frequency/high-amplitude cycles during the middle and late Pleistocene. Variations in aragonite content in the fine fraction of the periplatform ooze show a cyclic pattern throughout the Pleistocene, as previously observed in piston cores of the upper Pleistocene. These variations correlate well with the d18O record: high aragonite corresponds to light interglacial d18O values, and vice versa. Comparison of the d18O record and the aragonite curve helps to identify 23 interglacial and glacial oxygen-isotope stages, corresponding to 10.5 aragonite cycles (labeled A to K) commonly established during the middle and late Pleistocene (0.9 Ma-present). Strictly based on the aragonite curve, another 11 aragonite cycles, labeled L to V, were identified for the early Pleistocene (0.9 to 1.6 Ma). Mismatches between the d18O record and the aragonite curve occur mainly at some of the glacial-to-interglacial transitions, where aragonite increases usually lag behind d18O depletion. When one visually connects the minima on the Pleistocene aragonite curve, low-frequency (0.4 to 0.5 m.y.) supercycles seem to be superimposed on the high-frequency cycles. The timing of this supercycle roughly matches the timing of the Pleistocene carbonate preservation supercycles described in the Pacific, Indian, and Atlantic oceans. Mismatches between aragonite and d18O cycles are even more obvious for the late Pliocene (1.6 to 2.15 Ma). Irregular aragonite variations are observed for the late Pliocene, although after the onset of late Pleistocene-like glaciations in the North Atlantic Ocean 2.4 m.y. ago the d18O record has shown a mode of high-frequency/low-amplitude cycles. Initiation of climatically induced aragonite cycles occurs only at the Pliocene-Pleistocene transition, 1.6 m.y. ago. After that time, aragonite cycles are fully developed throughout the Quaternary. The 11-m-thick periplatform sequence below the hiatus represents a lower Pliocene interval between 3.75 and 4.45 Ma. The bottom half (4.25-4.45 Ma) has a fairly constant, high aragonite content (averaging 60%) and high sedimentation rates (28 m/m.y.) and corresponds to the end of the prolonged early Pliocene interglacial interval (4.1-5.0 Ma), established as a worldwide high sea-level stand. The second half (3.75-4.25 Ma), in which aragonite content decreases by successive steps, paralleled by a gradual 5180 enrichment in Globigerinoides sacculifera and low sedimentation rates (10 m/m.y), corresponds to the climatic deterioration established worldwide between 4.1 and 3.8 Ma, to a decrease of carbonate preservation observed in the equatorial Pacific Ocean, and to a global sea-level decline. Dolomite, a ubiquitous secondary component in the lower Pliocene, is interpreted as being authigenic and possibly related to diagenetic transformation of primary bank-derived fine magnesian calcite. Transformation of the primary mineralogical composition of the periplatform ooze was evidently minor, as the sediments have retained a detailed record of the Pliocene-Pleistocene climatic evolution. Clear evidence of diagenetic transformations in the periplatform ooze includes (1) the disappearance of magnesian calcite in the upper 20 m of Hole 633A, (2) the occurrence of calcite overgrowths on foraminiferal tests and microclasts at intermittent chalky core levels, and (3) the ubiquitous presence of authigenic dolomite in the lower Pliocene.

Stable oxygen isotope data of Globigerinoides ruber white and titanium intensity from sediment core GeoB6211-2

The South American summer monsoon (SASM) is the main source of precipitation for the most densely populated and agriculturally productive regions of tropical and subtropical South America. Here we investigate the impact of the Atlantic Multidecadal Oscillation (AMO) on the SASM using ~4500 yr long proxy records of the discharge variability of the La Plata River Drainage Basin (PRDB), subtropical South America. We measured the stable oxygen composition of planktic foraminifera (related to the extension of the PRDB plume), and Ti intensity in bulk sediment (related to the source of the terrigenous sediments) from a marine sediment core. Spectral and wavelet analyses of our records indicate an oscillation with period of ~64 yr. We conclude that the observed oscillation reflects variability in the SASM activity associated to the AMO. Sea surface temperature and atmospheric circulation anomalies triggered by the AMO would control the variability in SASM activity.

Pliocene-Pleistocene stack of globally distributed benthic stable oxygen isotope records

We present a 5.3-Myr stack (the ''LR04'' stack) of benthic d18O records from 57 globally distributed sites aligned by an automated graphic correlation algorithm. This is the first benthic delta18O stack composed of more than three records to extend beyond 850 ka, and we use its improved signal quality to identify 24 new marine isotope stages in the early Pliocene. We also present a new LR04 age model for the Pliocene-Pleistocene derived from tuning the delta18O stack to a simple ice model based on 21 June insolation at 65 N. Stacked sedimentation rates provide additional age model constraints to prevent overtuning. Despite a conservative tuning strategy, the LR04 benthic stack exhibits significant coherency with insolation in the obliquity band throughout the entire 5.3 Myr and in the precession band for more than half of the record. The LR04 stack contains significantly more variance in benthic delta18O than previously published stacks of the late Pleistocene as the result of higher resolution records, a better alignment technique, and a greater percentage of records from the Atlantic. Finally, the relative phases of the stack's 41- and 23-kyr components suggest that the precession component of delta18O from 2.7-1.6 Ma is primarily a deep-water temperature signal and that the phase of d18O precession response changed suddenly at 1.6 Ma.

Whole rock analytical techniques and glas analytical techniques of silicic magmas from the South East Rift, Manus Basin

There has been much recent interest in the origin of silicic magmas at spreading centres away from any possible influence of continental crust. Here we present major and trace element data for 29 glasses (and 55 whole-rocks) sampled from a 40 km segment of the South East Rift in the Manus Basin that span the full compositional continuum from basalt to rhyolite (50-75 wt % SiO2). The glass data are accompanied by Sr-Nd-Pb, O and U-Th-Ra isotope data for selected samples. These overlap the ranges for published data from this part of the Manus Basin. Limited increases in Cl/K ratios with increasing SiO2, La-SiO2 and Yb-SiO2 relationships, and the oxygen isotope data rule out models in which the more silicic lavas result from partial melting of altered oceanic crust or altered oceanic gabbros. Rather, the data form a coherent array that is suggestive of closed-system fractional crystallization and this is well simulated by MELTS models run at 0.2 GPa and QFM (quartz-fayalite-magnetite buffer) with 1 wt % H2O, using a parental magma chosen from the basaltic glasses. Although some assimilation of altered oceanic crust or gabbro cannot be completely ruled out, there is no evidence that this plays an important role in the origin of the silicic lavas. The U-series disequilibria are dominated by 238U and 226Ra excesses that limit the timescale of differentiation to less than a few millennia. Overall, the data point to rapid evolution in relatively small magma lenses located near the base of thick oceanic crust; we speculate that this was coupled with relatively low rates of basaltic recharge. A similar model may be applicable to the generation of silicic magmas elsewhere in the ocean basins.

Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.