South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

Rare earth elements in standard samples of ocean Fe-Mn nodules and crusts

Contents of rare earth elements (REE) in standard samples of Fe-Mn nodules (SDO-5, 6), Fe-Mn crust (SDO-7), and red clay (SDO-9) have been determined by ICP-MS and instrumental neutron activation analysis. Reproducibility of ICP-MS was 5-6%. These results are discussed and compared with other data. It has been found that distribution of REE in the standard samples of ocean Fe-Mn ores and red clay is highly homogenous.

Geochemistry of rare earth elements in basalts from Walvis Ridge

Selected basalts from a suite of dredged and drilled samples (IPOD sites 525, 527, 528 and 530) from the Walvis Ridge have been analysed to determine their rare earth element (REE) contents in order to investigate the origin and evolution of this major structural feature in the South Atlantic Ocean. All of the samples show a high degree of light rare earth element (LREE) enrichment, quite unlike the flat or depleted patterns normally observed for normal mid-ocean ridge basalts (MORBs). Basalts from Sites 527, 528 and 530 show REE patterns characterised by an arcuate shape and relatively low (Ce/Yb)N ratios (1.46-5.22), and the ratios show a positive linear relationship to Nb content. A different trend is exhibited by the dredged basalts and the basalts from Site 525, and their REE patterns have a fairly constant slope, and higher (Ce/Yb)N ratios (4.31-8.50). These differences are further reflected in the ratios of incompatible trace elements, which also indicate considerable variations within the groups. Mixing hyperbolae for these ratios suggest that simple magma mixing between a 'hot spot' type of magma, similar to present-day volcanics of Tristan da Cunha, and a depleted source, possibly similar to that for magmas being erupted at the Mid-Atlantic Ridge, was an important process in the origin of parts of the Walvis Ridge, as exemplified by Sites 527, 528 and 530. Site 525 and dredged basalts cannot be explained by this mixing process, and their incompatible element ratios suggest either a mantle source of a different composition or some complexity to the mixing process. In addition, the occurrence of different types of basalt at the same location suggests there is vertical zonation within the volcanic pile, with the later erupted basalts becoming more alkaline arid more enriched in incompatible elements. The model proposed for the origin and evolution of the Walvis Ridge involves an initial stage of eruption in which the magma was essentially a mixture of enriched and depleted end-member sources, with the N-MORB component being small. The dredged basalts and Site 525, which represent either later-stage eruptives or those close to the hot spot plume, probably result from mixing of the enriched mantle source with variable amounts and variable low degrees of partial melting of the depleted mantle source. As the volcano leaves the hot spot, these late-stage eruptives continue for some time. The change from tholeiitic to alkalic volcanism is probably related either to evolution in the plumbing system and magma chamber of the individual volcano, or to changes in the depth of origin of the enriched mantle source melt, similar to processes in Hawaiian volcanoes.

Rare-earth elements and isotope ratios at DSDP Leg 82 Holes

We report 48 analyses of rare-earth elements (REE) and 15 143Nd/144Nd and 87Sr/86Sr analyses for basalts from the eight holes drilled during Leg 82. Discrete and distinct REE patterns and 143Nd/144Nd ratios characterize the eight holes, with little variation observed downhole except in Holes 561 and 558, thus suggesting dominantly long-term temporal and large-scale spatial variations in the mantle source of these basalts beneath the Mid-Atlantic Ridge over the last 35 Ma of its spreading activity. There is a good inverse correlation between 143Nd/144Nd and (La/Sm)EF with one exception in Hole 558 (approximately 35 Ma), the latter suggesting a recent (35 Ma) light REE depletion event, perhaps caused by dynamic or fractional melting. Short-term temporal and small-scale spatial mantle source variability is also evident in Hole 561 (approximately 18 Ma), which has rapid fluctuations in REE patterns and 143Nd/144Nd ratios (suggesting rapid transfer of magma from the time of melting) and is evidence contrary to the presence of a well-mixed magma chamber at this particular site and time. The mantle source variations noted can be interpreted within two extreme models. The first model invokes a convecting mantle depleted in large ion lithophile elements (LILE) and containing lumps (or veins) of LILE-enriched material of various shapes and sizes, passively and randomly distributed throughout. A second more restrictive model considers the interaction of fixed mantle plumes and the LILE-depleted asthenosphere flowing towards a migrating Mid- Atlantic Ridge (MAR) axis. With the exception of Hole 558 and the uncertainties of reconstructions of absolute plate movements in the region, the observed variations can be explained by two hot spots; the nearly ridge-centered Azores hot spot (plume) and another hot spot located beneath the African plate that may be affecting the source of basalts currently erupting at the MAR axis at 35°N and which, in the past, would have produced the New England chain of seamounts on the North American plate and (later) the Atlantis-Great Meteor chain on the African plate. Basalts erupted south of the Hayes Fracture Zone have not been affected by either of these two hot spots over the last 35 Ma and appear to have been continuously derived from the LILE-depleted source. Subaxial flow downridge from the Azores plume appears to have started 9 Ma, on the basis of the southward converging V-shaped time-transgressive ridges branching from the Pico and Corves Island, or not earlier than 16 Ma, on the basis of the geochemical results. Variations within Hole 558 remains unexplained by the latter model, unless we hypothesize a third hot spot.