Fe isotopic composition in continental iron cycle (Table 1)

The effect of continental weathering on the iron isotope compositions of natural materials is investigated. Unweathered igneous rocks, pelagic clay, and dust fall within the range delta56Fe=0 +/- 0.3 per mil. Rivers with large suspended loads also have delta56Fe values near zero. Dilute streams have delta56Fe values that trend towards lower delta56Fe (~-1) suggesting that dissolved riverine iron is isotopically light relative to igneous rocks. Bulk soil and soil leaches display systematically different delta56Fe profiles, indicating that isotopically distinct Fe pools are generated during pedogenesis. Nannofossil ooze, which contains Fe scavenged from the ocean water column, has delta56Fe c. 0, but is consistent with seawater dissolved Fe having negative delta56Fe. It is inferred that continental weathering under modern oxidizing Earth surface conditions preferentially releases dissolved Fe with negative delta56Fe, which is transported in rivers to the ocean. A preliminary analysis of the marine Fe budget suggests that riverine Fe has a substantial role in determining the delta56Fe of both the modern and ancient oceans, but other inputs, particularly that from diagenesis of marine sediments, may also be important. Since the chemical pathways of Fe processing during weathering are dependent on oxidation state and biological activity, Fe isotopes may prove useful for detecting changes in these parameters in the geologic past.

Nd, Pb and Sr isotopes in sediment cores from the Gulf of Cadiz and the Portuguese margin

Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.

Geochemistry of Southern Ocean sediments

Reconstructing past detrital flux and provenance in the Southern Ocean provides information about changes in source regions associated with climate variations and transport pathways. We present a Last Glacial Maximum (LGM) to Holocene comparison of 230Th normalised fluxes combined with sediment provenance data (Pb, Nd and Sr isotopes) from a latitudinal core transect in the eastern Atlantic sector of the Southern Ocean (ODP Leg 177 cores). We compare the radiogenic isotopic composition (IC) of detritus in these cores to that of cores proximal to potential source areas. We observe a well-defined latitudinal Holocene gradient in both detrital flux and provenance of sediment. High detrital fluxes in the north are associated with terrigenous material derived from southern Africa, while low detrital fluxes in the south are associated with supply from southern South America, West Antarctica and the South Sandwich Islands. The data suggest that this well-defined Holocene gradient in detrital flux and sediment provenance is controlled by the flow of the Antarctic Circumpolar Current (ACC) and the position of its frontal zones. The LGM is characterised by 2 to 6 times higher than modern detrital fluxes at most ODP Leg 177 sites. The LGM detrital fluxes do not show a latitudinal trend and suggest a greater supply of glaciogenic detritus sourced from southern South America. Glacial Patagonian outwash sediments (< 5 µm fraction) were analysed and compared to the bulk compositions of the marine sediments. The Pb IC of the Patagonian sediments is very similar to the glacial IC of sediments in the Scotia Sea and at ~ 49° S latitude in the eastern Atlantic sector. We propose that the glacial IC of sediments is controlled by increased delivery of Patagonian detritus initially supplied by glaciers and then transported at depth via the ACC.

(Table S1) Calcium isotope ratios of Pacific Ocean sediments

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the d44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Radiogenic isotope record of Arctic Ocean circulation and weathering inputs of the past 15 million years

Lead (Pb), neodymium (Nd), and strontium (Sr) isotopic analyses were carried out on sediment leachates (reflecting the isotope composition of past seawater) and digests of the bulk residues (reflecting detrital continental inputs) of Integrated Ocean Drilling Program (IODP) Leg 302 and core PS2185 from the Lomonosov Ridge (Arctic Ocean). Our records are interpreted to reflect changes in continental erosion and oceanic circulation, driven predominantly by tectonic forcing on million-year timescales in the older (pre-2 Ma) part of the record and by climatic forcing of weathering and erosion of the Eurasian continental margin on thousand-year timescales in the younger (post-2 Ma) part. These data, covering the past ~15 Ma, show that continental inputs to the central Arctic Ocean have been more closely linked to glacial and hydrological processes occurring on the Eurasian margin than on continental North America and Greenland. The constancy of the detrital input signatures supports the early existence of an Arctic sea ice cover, whereas the major initiation of Northern Hemisphere glaciation at 2.7 Ma appears to have had little impact on the weathering regime of the Eurasian continental margin.

Nd, Sr and Pb isotopes and clay minerals in sediment cores from the Gulf of Cadiz and the Portuguese margin

The assemblages of marine sediments on the SW Iberian shelf have been controlled by contributions from distinct sources, which have varied in response to environmental changes since the Last Glacial Maximum (LGM). The rapid, decadal scale Mediterranean overturning circulation permits mixing of suspended particles from the entire Mediterranean Sea. They are entrained into the suspended particulate matter (SPM) carried by Mediterranean Outflow Water (MOW), which enters the eastern North Atlantic through the Strait of Gibraltar and spreads at intermediate depths in the Gulf of Cadiz and along the Portuguese continental margin. Other major sediment sources that have contributed to the characteristics and budget of SPM along the flow path of MOW on the SW Iberian shelf are North African dust and river-transported particles from the Iberian Peninsula. To reconstruct climate- and circulation-driven changes in the supply of sediments over the past ~23000 cal yr B.P., radiogenic Nd, Sr and Pb isotope records of the clay-size sediment fraction were obtained from one gravity core in the Gulf of Cadiz (577 m water depth) and from two gravity cores on the Portuguese shelf (1745 m, 1974 m water depth). These records are supplemented by time series analyses of clay mineral abundances from the same set of samples. Contrary to expectations, the transition from the LGM to the Holocene was not accompanied by strong changes in sediment provenance or transport, whereas Heinrich Event 1 (H1) and the African Humid Period (AHP) were marked by significantly different isotopic signatures reflecting changes in source contributions caused by supply of ice rafted material originating from the North American craton during H1 and diminished supply of Saharan dust during the AHP. The data also reveal that the timing of variations in the clay mineral abundances was decoupled from that of the radiogenic isotope signatures.

d11B and metal/Ca ratios versus size fractions in the Surface and deep dwelling species, ODP Holes 130-806B and 108-664C

We have assessed the reliability of several foraminifer-hosted proxies of the ocean carbonate system (d11B, B/Ca, and U/Ca) using Holocene samples from the Atlantic and Pacific oceans. We examined chemical variability over a range of test sizes for two surface-dwelling foraminifers (Globigerinoides sacculifer and Globigerinoides ruber). Measurements of d11B in G. ruber show no significant relationship with test size in either Atlantic or Pacific sites and appear to provide a robust proxy of surface seawater pH. Likewise there is no significant variability in the d11B of our Atlantic core top G. sacculifer, but we find that d11B increases with increasing test size for G. sacculifer in the Pacific. These systematic differences in d11B are inferred to be a consequence of isotopically light gametogenic calcite in G. sacculifer and its preferential preservation during postdepositional dissolution. The trace element ratio proxies of ocean carbonate equilibria, U/Ca and B/Ca, show systematic increases in both G. ruber and G. sacculifer with increasing test size, possibly as a result of changing growth rates. This behavior complicates their use in paleoceanographic reconstructions. In keeping with several previous studies we find that Mg/Ca ratios increase with increasing size fraction in our well-preserved Atlantic G. sacculifer but not in G. ruber. In contrast to previous interpretations we suggest that these observations reflect a proportionally larger influence of compositionally distinct gametogenic calcite in small individuals compared to larger ones. As with d11B this influences G. sacculifer but not G. ruber, which has negligible gametogenic calcite.

(Table 1) Cadmium and nutrient concentration of surface waters sampled during POLARSTERN cruise ANT-XXIV/III

The High Nutrient Low Chlorophyll (HNLC) Southern Ocean plays a key role in regulating the biological pump and the global carbon cycle. Here we examine the efficacy of stable cadmium (Cd) isotope fractionation for detecting differences in biological productivity between regions. Our results show strong meridional Cd isotope and concentration gradients modulated by the Antarctic Fronts, with a clear biogeochemical divide located near 56°S. The coincidence of the Cd isotope divide with the Southern Boundary of the Antarctic Circumpolar Current (ACC),together with evidence for northward advection of the Cd signal in the ACC, demonstrate that Cd isotopes trace surface ocean circulation regimes. The relationships between Cd isotope ratios and concentrations display two negative correlations, separating the ACC and Weddell Gyre into two distinct Cd isoscapes. These arrays are consistent with Rayleigh fractionation and imply a doubling of the isotope effect due to biological consumption of Cd during water transport from the Weddell Gyre into the ACC. The increase in magnitude of Cd isotope fractionation can be accounted for by differences in the phytoplankton biomass, community composition, and their physiological uptake mechanisms in the Weddell Gyre and ACC, thus linking Cd isotope fractionation to primary production and the global carbon cycle.

Geochemistry and radiogenic isotope ratios of the volcanic sequences from Izu-Bonin Arc, Japan

New radiogenic isotope and trace element data are presented for the volcanic sequences along 600 km of the active Izu-Bonin arc, the Oligocene Izu arc, and their associated rift basins. As with many intra-oceanic island arcs, the Pliocene-Recent Izu-Bonin frontal-arc lavas are highly depleted in Zr, Nb and the rare-earth elements relative to typical mid-ocean ridge basalt (MORB), indicating that the mantle wedge source has undergone a previous episode of melting. Ratios between these elements (such as Nb/Zr and La/Sm), as well as 143Nd/144Nd, do not vary significantly along the length of the frontal-arc. These parameters suggest that each of the arc volcanoes is derived from similar melt fractions of the mantle wedge. However, Ba/Zr, Ba/Rb and 87Sr/86Sr increase along the frontal-arc to the north. This leads us to propose that a variable enrichment in Ba and radiogenic Sr is superimposed on the mantle wedge. Sr-Nd and Pb-Nd isotope variation indicate that both Sr and Pb become more radiogenic after fluid addition. However, Pb isotope ratios do not correlate with increases in Pb concentration or ratios such as Ba/Zr and Nb/Pb. In other words, the Pb isotopic composition of the arc lavas appears to be independent of the amount of Pb introduced by subduction fluids into the mantle source. This buffering of Pb isotopes along the frontal-arc means that the isotopic composition of the lavas is indistinguishable from that of the fluid. Isotopic mixing models presented for the arc are only illustrative of the many plausible combinations of components and quantities. Despite this, we are able to determine that the mantle wedge has isotopic characteristics similar to Indian Ocean MORB, and that the subduction-fluid solute is primarily derived from subducted oceanic basalt with a <2% contribution from subducted sediment. Lavas in the Oligocene Izu arc and fore-arc basin were derived from a mantle wedge of similar composition to the active arc. Despite levels of Pb enrichment comparable to those of the modern arc, the Pb isotopes of the Oligocene volcanics indicate a lower sediment input into the melting region.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.