(Table 1) Isotopic and trace-element composition of ODP Leg 127/128 basalts

The western Pacific includes many volcanic island arc and backarc complexes, yet multi-isotopic studies of them are rare. Basement rocks of the Sea of Japan backarc basin were encountered at Sites 794,795, and 797, and consisted of basaltic sills and lava flows. These rocks exhibit a broad range in isotopic composition, broader than that seen in any other western Pacific arc or backarc system: 87Sr/86Sr = 0.70369 to 0.70499, 143Nd/144Nd = 0.51267 to 0.51317, 206Pb/204Pb = 17.64 to 18.36. The samples form highly correlated arrays between very depleted mid-ocean ridge basalt (MORB) and the Pacific pelagic sediment fields on Pb-Pb plots. Similarly, on plots of Sr-Pb and Nd-Pb, the Sea of Japan samples lie on mixing curves between depleted mantle and enriched mantle ("EM II"), which is interpreted to be of average crustal or pelagic sediment composition. The source of these backarc rocks appears to be a MORB-like mantle source, contaminated by pelagic sediments. Unlike the Mariana and Izu arc/backarc systems, Japanese arc and backarc rocks are indistinguishable from each other in a Sr-Nd isotope plot, and have similar trends in Pb-Pb plots. Thus, sediment contamination of the mantle wedge appears to control the isotopic compositions of both the arc and backarc magmas. Two-component mixing calculations suggest that the percentage of sediments in the magma source varies from 0.5% to 2.5%.

Bulk calcite minor element composition of ODP Leg 130 samples

We investigated minor element ratios (Sr/Ca and Mg/Ca) in bulk sediment samples from Sites 803-807 using a recently optimized sample treatment protocol for calcium-carbonate-rich sediments consisting of sequential reductive and ion exchange treatments. We evaluated this protocol relative to bulk sediment leaching using samples from Sites 804 and 806, the two end-member sites in the depth transect, reporting as well Mn/Ca and Fe/Ca ratios for sediments from these two sites processed by means of both methods. The Sr/Ca ratios were only slightly affected by the sample treatment, with an average reduction of 6%-7% caused primarily by the ion exchange step. The reductive sample treatment, designed to be effective at removing Mn-rich oxyhydroxides, has a major effect on Mg/Ca ratios, with up to 50% reduction, whereas little effect occurred in ion exchange alone on Mg/Ca ratios. The Mn/Ca and Fe/Ca ratios were not consistently offset by the sample treatment, and these ratios do not appear to be representative of calcite geochemistry reflecting either ocean history or diagenetic overprinting. Celestite solubility appears to be an important control on interstitial water Sr concentrations in these sites, and it must be considered when constructing Sr mass balance models of calcite recrystallization. Calcite Sr/Ca ratios (range 1-2 mmol/mol) are similar from site to site when plotted vs. age, with a pattern comparable to that for well-preserved foraminifer tests over the past 40 Ma. Interstitial water Mg and Ca gradients appear to reflect basement character and the intensity of alteration; they can vary substantially over a small area. Calcite Mg/Ca ratios (range 1.5-4.5 mmol/mol) differ from site to site, with generally higher ratios for sites at a shallower water depth. Increasing calcite Mg/Ca ratios correlate with decreasing Sr/Ca ratios in the treated samples. No consistent pattern exists for calcite Mg/Ca ratios vs. age or depth, nor is any direct correlation to interstitial water Mg/Ca ratios present.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Trace element ratios of Globigerina bulloides from the southwest Pacific Ocean

We present Mg/Ca data for Globigerina bulloides from 10 core top sites in the southwest Pacific Ocean analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Mg/Ca values in G. bulloides correlate with observed ocean temperatures (7°C-19°C), and when combined with previously published data, an integrated Mg/Ca-temperature calibration for 7°C-31°C is derived where Mg/Ca (mmol/mol) = 0.955 * e**(0.068 * T) (r**2 = 0.95). Significant variability of Mg/Ca values (20%-30%) was found for the four visible chambers of G. bulloides, with the final chamber consistently recording the lowest Mg/Ca and is interpreted, in part, to reflect changes in the depth habitat with ontogeny. Incipient and variable dissolution of the thin and fragile final chamber, and outermost layer concomitantly added to all chambers, caused by different cleaning techniques prior to solution-based ICPMS analyses, may explain the minor differences in previously published Mg/Ca-temperature calibrations for this species. If the lower Mg/Ca of the final chamber reflects changes in depth habitat, then LA-ICPMS of the penultimate (or older) chambers will most sensitively record past changes in near-surface ocean temperatures. Mean size-normalized G. bulloides test weights correlate negatively with ocean temperature (T = 31.8 * e**(-30.5*wtN); r**2 = 0.90), suggesting that in the southwest Pacific Ocean, temperature is a prominent control on shell weight in addition to carbonate ion levels.

Trace element profiles of the sea anemone Anemonia viridis living nearby a natural CO2 vent

Ocean acidification (OA) is not an isolated threat, but acts in concert with other impacts on ecosystems and species. Coastal marine invertebrates will have to face the synergistic interactions of OA with other global and local stressors. One local factor, common in coastal environments, is trace element contamination. CO2 vent sites are extensively studied in the context of OA and are often considered analogous to the oceans in the next few decades. The CO2 vent found at Levante Bay (Vulcano, NE Sicily, Italy) also releases high concentrations of trace elements to its surrounding seawater, and is therefore a unique site to examine the effects of long-term exposure of nearby organisms to high pCO2 and trace element enrichment in situ. The sea anemone Anemonia viridis is prevalent next to the Vulcano vent and does not show signs of trace element poisoning/stress. The aim of our study was to compare A. viridis trace element profiles and compartmentalization between high pCO2 and control environments. Rather than examining whole anemone tissue, we analyzed two different body compartments-the pedal disc and the tentacles, and also examined the distribution of trace elements in the tentacles between the animal and the symbiotic algae. We found dramatic changes in trace element tissue concentrations between the high pCO2/high trace element and control sites, with strong accumulation of iron, lead, copper and cobalt, but decreased concentrations of cadmium, zinc and arsenic proximate to the vent. The pedal disc contained substantially more trace elements than the anemone's tentacles, suggesting the pedal disc may serve as a detoxification/storage site for excess trace elements. Within the tentacles, the various trace elements displayed different partitioning patterns between animal tissue and algal symbionts. At both sites iron was found primarily in the algae, whereas cadmium, zinc and arsenic were primarily found in the animal tissue. Our data suggests that A. viridis regulates its internal trace element concentrations by compartmentalization and excretion and that these features contribute to its resilience and potential success at the trace element-rich high pCO2 vent.

Major element concentration and radionuclides of equatorial Pacific deep-sea sediments

The (231Pa/230Th)xs,0 records obtained from two cores from the western (MD97-2138; 1°25'S, 146°24'E, 1900 m) and eastern (ODP Leg 138 Site 849, 0°11.59'N, 110°31.18'W, 3851 m) equatorial Pacific display similar variability over the last 85000 years, i.e. from isotopic stages 1 to 5a, with systematically higher values during the Holocene, isotopic stage 3 and isotopic stage 5a, and lower values, approaching the production rate ratio of the two isotopes (0.093), during the colder periods corresponding to isotopic stages 2 and 4. We have also measured the 230Th-normalized biogenic preserved and terrigenous fluxes, as well as major and trace elements concentrations, in both cores. The (231Pa/230Th)xs,0 results combined with the changes in preserved carbonate and opal fluxes at the eastern site indicate lower productivity in the eastern equatorial Pacific during glacial periods. The (231Pa/230Th)xs,0 variations in the western equatorial Pacific (WEP) also seem to be controlled by productivity (carbonate and/or opal). The generally high (231Pa/230Th)xs,0 ratios (>0.093) of the profile could be due to opal and/or MnO2 in the sinking particles. The profiles of (231Pa/230Th)xs,0 and 230Th-normalized fluxes indicate a decrease in exported carbonate, and possibly opal, during isotopic stages 2 and 4 in MD97-2138. Using 230Th-normalized flux, we also show that sediments from the two cores were strongly affected by sediment redistribution by bottom currents suggesting a control of mass accumulation rates by sediment focusing variability.

(Table S1) Original element/Ca data for the OGA and Tahiti corals

[1] Previous studies have demonstrated the potential for the Li content of coral aragonite to record information about environmental conditions, but no detailed study of tropical corals exists. Here we present the Li and Mg to Ca ratios at a bimonthly to monthly resolution over 25 years in two modern Porites corals, the genus most often used for paleoclimate reconstructions in the tropical Indo-Pacific. A strong relationship exists between coral Li/Ca and locally measured SST, indicating that coral Li/Ca can be used to reconstruct tropical SST variations. However, Li/Ca ratios of the skeleton deposited during 1979-1980 do not track local SST well and are anomalously high in places. The Mg/Ca ratios of this interval are also anomalously high, and we suggest Li/Ca can be used to reconstruct tropical SST only when Mg/Ca data are used to carefully screen for relatively rare biological effects. Mg/Li or Li/Mg ratios provide little advantage over Li/Ca ratios, except that the slope of the Li/Mg temperature relationship is more similar between the two corals. The Mg/Li temperature relationship for the coral that experienced a large temperature range is similar to that found for cold water corals and aragonitic benthic foraminifera in previous studies. The comparison with data from other biogenic aragonites suggests the relationship between Li/Mg and water temperature can be described by a single exponential relationship. Despite this hint at an overarching control, it is clear that biological processes strongly influence coral Li/Ca, and more calibration work is required before widely applying the proxy.

Bulk sediment element analysis of sediment cores GeoB10065-9 and GeoB10065-7, offshore northwest Sumba Island, Indonesia

The Australian-Indonesian monsoon has a governing influence on the agricultural practices and livelihood in the highly populated islands of Indonesia. However, little is known about the factors that have influenced past monsoon activity in southern Indonesia. Here, we present a ~6000 years high-resolution record of Australian-Indonesian summer monsoon (AISM) rainfall variations based on bulk sediment element analysis in a sediment archive retrieved offshore northwest Sumba Island (Indonesia). The record suggests lower riverine detrital supply and hence weaker AISM rainfall between 6000 yr BP and ~3000 yr BP compared to the Late Holocene. We find a distinct shift in terrigenous sediment supply at around 2800 yr BP indicating a reorganization of the AISM from a drier Mid Holocene to a wetter Late Holocene in southern Indonesia. The abrupt increase in rainfall at around 2800 yr BP coincides with a grand solar minimum. An increase in southern Indonesian rainfall in response to a solar minimum is consistent with climate model simulations that provide a possible explanation of the underlying mechanism responsible for the monsoonal shift. We conclude that variations in solar activity play a significant role in monsoonal rainfall variability at multi-decadal and longer timescales. The combined effect of orbital and solar forcing explains important details in the temporal evolution of AISM rainfall during the last 6000 years. By contrast, we find neither evidence for volcanic forcing of AISM variability nor for a control by long-term variations in the El Niño-Southern Oscillation (ENSO).