Platinum group elements and geochemistry of altered oceanic crust of ODP Hole 140-504B

Primary chemical heterogeneity in the sheeted dike complex in Deep Sea Drilling Project Hole 504B makes these rocks unsuitable for conventional mass balance calculations in determining element mobility associated with hydrothermal alteration. Due to the original heterogeneity and variable degrees of fractionation in the dikes, an appropriate reference sample on which calculations can be based is difficult to find. Therefore, the use of incompatible element ratios is developed to evaluate geochemical changes during alteration(s). For example, on a Zr/Yb-La/Yb plot, scatter along a straight line suggests tapping of a variably depleted mantle source and deviation from the line suggests element mobility (gain or loss). Using this method, our data indicates that the hydrothermal evolution of the sheeted dike complex was accompanied by significant loss of Cu, Zn, and Ti and some loss of La. The sheeted dike complex has low platinum group element (PGE) concentrations and steep PGE patterns, typical of mid-ocean ridge basalts (MORBs) on the global scale. We propose that the unusual PGE patterns of MORBs cannot be entirely generated by a partial melting and sulfide segregation model; instead, these patterns in part must have been inherited from their mantle source. The Au data show no evidence for mobilization during hydrothermal alteration of the dikes.

Tab. 1: Geochemical analysis and age dating of Kap Washington Group volcanites and related dykes

The bimodal, alkaline volcanic suite of the Kap Washington Group (KWG) at the northern coast of Greenland was investigated during the BGR CASE 2 expedition in 1994. Geochemical and Nd and Sr isotopic data are presented for basalts to rhyolites of the KWG and of related basaltic dykes cutting Lower Paleozoic sediments. In the evd(t) vs. (87Sr/86Sr)t diagram, the KWG basalts and rhyolites follow a common mixing trend with increasing crustal contamination from basic to acid volcanites. Assimilation of pre-existing crustal rocks during formation of the rhyolitic melt is documented by Nd model ages of 0.9-1.2 Ga and by different fractionation trends for the basalts and the rhyolites in the Y vs. Zr diagram. Petrographical and geochemical features indicate intra-plate volcanism which was active most probably during a continental rifting phase. A new Rb/Sr whole rock age on rhyolites of 64 ±3 Ma, corresponding to the result of LARSEN (1982), confirms that the volcanic activity lasted until the Cretaceous-Tertiary boundary. 40Ar139Ar dating on amphibol separates from a comendite yielded strongly disturbed age spectra with a minimum age of 37.7 ±0.3 Ma. This age is interpreted to date a hydrothermal overprint of the volcanic rocks related to compressive tectonics which led to the overthrust of basement rocks over the Kap Washington Group.

Whale sightings, group sizes and krill biomass in West Greenland in 2005

This study combined data on fin whale Balaenoptera physalus, humpback whale Megaptera novaeangliae, minke whale B. acutorostrata, and sei whale B. borealis sightings from large-scale visual aerial and ship-based surveys (248 and 157 sightings, respectively) with synoptic acoustic sampling of krill Meganyctiphanes norvegica and Thysanoessa sp. abundance in September 2005 in West Greenland to examine the relationships between whales and their prey. Krill densities were obtained by converting relationships of volume backscattering strengths at multiple frequencies to a numerical density using an estimate of krill target strength. Krill data were vertically integrated in 25 m depth bins between 0 and 300 m to obtain water column biomass (g/m**2) and translated to density surfaces using ordinary kriging. Standard regression models (Generalized Additive Modeling, GAM, and Generalized Linear Modeling, GLM) were developed to identify important explanatory variables relating the presence, absence, and density of large whales to the physical and biological environment and different survey platforms. Large baleen whales were concentrated in 3 focal areas: (1) the northern edge of Lille Hellefiske bank between 65 and 67°N, (2) north of Paamiut at 63°N, and (3) in South Greenland between 60 and 61° N. There was a bimodal pattern of mean krill density between depths, with one peak between 50 and 75 m (mean 0.75 g/m**2, SD 2.74) and another between 225 and 275 m (mean 1.2 to 1.3 g/m**2, SD 23 to 19). Water column krill biomass was 3 times higher in South Greenland than at any other site along the coast. Total depth-integrated krill biomass was 1.3 x 10**9 (CV 0.11). Models indicated the most important parameter in predicting large baleen whale presence was integrated krill abundance, although this relationship was only significant for sightings obtained on the ship survey. This suggests that a high degree of spatio-temporal synchrony in observations is necessary for quantifying predator-prey relationships. Krill biomass was most predictive of whale presence at depths >150 m, suggesting a threshold depth below which it is energetically optimal for baleen whales to forage on krill in West Greenland.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.