Chemical composition of ocean-floor basalts and separated magnetites DSDP Legs 37, 45 and 46

Titanomagnetites separated from 15 different rock samples (including ocean-floor basalts from DSDP Legs 37, 45 and 46) were analyzed together with whole-rock samples by instrumental neutron-activation analysis for Sc, Cr, Co, Zn, Hf, Ta, Th and the REE La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Tm, Yb and Lu. In titanomagnetities from ocean-floor basalts and some other rocks, REE are enriched with respect to the whole-rock composition by factors of between 1.5 and 3 for light REE and between 1.0 and 1.9 for heavy REE; that is, REE with larger ionic radii are preferentially incorporated into the magnetite lattice. Three magnetite samples are REE depleted. Their whole-rock samples contain P in appreciable amounts, so apatite, an important REE-accumulating mineral, could have captured REE to some extent. All titanomagnetites show a marked negative Eu anomaly, this is most probably caused by discrimination of Eu(2+) from the magnetite lattice. Co, Zn, Hf and Ta are significantly enriched in magnetites. The distribution behaviour of Sc and Cr is masked chiefly by the crystallization of clinopyroxene and therefore is not easy to estimate. Ulvöspinel contents of about 70% for the titanomagnetites from ocean-floor basalts were estimated from qualitative microprobe analysis. Ulvöspinel contents of all other samples varied in a wide range from 20% to about 90%. No correlation could be observed between this and the REE contents of the magnetites. Ilmenite exsolution lamellae could only be observed in titanomagnetites from a doleritic basalt from Leg 45.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Diagenetic development of deep-sea carbonate sediments from DSDP Holes 30-228, 30-289 and 33-316

Laboratory measurements of ultrasonic velocity (VP, VS) and attenuation (QP**-1, QS**-1) in deep-sea carbonate sequences at DSDP Sites 288, 289 and 316 in the equatorial Pacific were made in conjunction with studies of sediment density, porosity and pore geometry in order to investigate the role of diagenesis in the development of physical properties. Bulk porosity decrease appears to be related more significantly to depth of burial than to age of strata. Both depth of burial and age, however, are important factors controlling the modal pore diameter. In deep-burial diagenesis the modification of pore geometry is influenced by the presence of silica during diagenesis. In carbonate sequences at the three DSDP sites studied, shear wave attenuation anisotropy (QSHH**-1/QSHV**-1) correlates with the shear wave velocity anisotropy. Pore orientation, resulting from overburden pressure and other deep-burial diagenetic processes, is an important factor controlling the increase of VP anisotropy with age and depth of burial. On the basis of observed minor changes in anisotropy values with increasing pressure for some samples, other contributions to VP anisotropy such as grain orientation and bedding lamination cannot be ruled out.