In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Major element oxides of minerals from a lava pond at ODP Site 206-1256

At Ocean Drilling Program Site 1256 (6°44.2'N, 91°56.1'W), during Leg 206, a thick massive unit was cored in two neighboring penetrations of the uppermost basement, Holes 1256C and 1256D. This thick massive lava flow, commonly referred to as the "Lava Pond," is identified as Unit 18 (>30 m thick) in Hole 1256C and Unit 1 (>74.2 m thick) in Hole 1256D (Wilson et al., 2003, doi:10.2973/odp.proc.ir.206.2003). In the coarse-grained basalt that comprises this lithological unit, low-temperature "background" alteration events are present. This report provides microprobe analyses of both primary and secondary minerals present in this massive lava pond. The analyses of typically magmatic minerals (titanomagnetite, plagioclase, and clinopyroxene) are given for comparison with secondary minerals.

Age and chemical composition of apatites from five DSDP and ODP Sites in the Pacific, Atlantic and Indian Oceans

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ~10° and 70°C over geological time scales of ~15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analyzed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30°C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 µm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30°C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ~30°C. For samples which experienced maximum temperatures between ~30 and 70°C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.

Fission track analyses of ODP Hole 129-800A samples

Four models of fission track annealing in apatite are compared with measured fission track lengths in samples from Site 800 in the East Mariana Basin, Ocean Drilling Program Leg 129, given an independently determined temperature history. The temperature history of Site 800 was calculated using a one-dimensional, compactive, conductive heat flow model assuming two end-member thermal cases: one for cooling of Jurassic ocean crust that has experienced no subsequent heating, and one for cooling of Cretaceous ocean crust. Because the samples analyzed were only shallowly buried and because the tectonic history of the area since sample deposition is simple, resolution of the temperature history is high. The maximum temperature experienced by the sampled bed is between 16°-21°C and occurs at 96 Ma; temperatures since the Cretaceous have dropped in spite of continued pelagic sediment deposition because heat flow has continued to decay exponentially and bottom-water temperatures have dropped. Fission tracks observed within apatite grains from the sampled bed are 14.6 +/- 0.1 µm (1 sigma) long. Given the proposed temperature history of the samples, one unpublished and three published models of fission track annealing predict mean track lengths from 14.8 to 15.9 µm. These models require temperatures as much as 40°C higher than the calculated paleotemperature maximum of the sampled bed to produce the same degree of track annealing. Measured and predicted values are different because annealing models are based on extrapolation of high temperature laboratory data to geologic times. The model that makes the closest prediction is based on the greatest number of experiments performed at low temperature and on an apatite having composition closest to that of the core samples.

Physics, geochemistry and bulk sedimentology on cores from the Peru Basin

Empirical relationships between physical properties determined non-destructively by core logging devices and calibrated by carbonate and opal measurements determined on discrete samples allow extraction of carbonate and opal records from the non-destructive measurements in biogenic settings. Contents of detrital material can be calculated as a residual. For carbonate and opal the correlation coefficients (r) are 0.954 and ?0.916 for sediment density, ?0.816 and 0.845 for compressional-wave velocity, 0.908 and ?0.942 for acoustic impedance, and 0.886 and ?0.865 for sediment color (lightness). Carbonate contents increase in concert with increasing density and acoustic impedance, decreasing velocity and lighter sediment color. The opposite is true for opal. The advantages of deriving the sediment composition quantitatively from core logging are: (i) sampling resolution is increased significantly, (ii) non-destructive data can be gathered rapidly, and (iii) laboratory work on discrete samples can be reduced. Applied to paleoceanographic problems, this method offers the opportunity of precise stratigraphic correlations and of studying processes related to biogenic sedimentation in more detail. Density is most promising because it is most strongly affected by changes in composition.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

(Table 1) Chemical composition of plagioclase and amphibole-pyroxene containing samples from pyroxene-amphibole-asbestos rock collected in the Hess Deep

Recent sediments with distinct signs of hydrothermal alteration sampled in the Hess Deep(Galapagos Ridge, East Pacific Rise) contained a piece of ash-gray rock, which differed from other rock fragments by degree of consolidation, conchoidal fracture, and had properties of asbestos. Our studies found that the sample represented mixture of asbestos-like pyroxene of diopside-hedenbergite composition, amphibole of tremolite composition and a new mineral, which basic structure consisted of bands of triple pyroxene chains with the radical [Si6O16]. The latter can be regarded as intermediate between amphiboles and layered silicates. Also in some parts of the sample presence of trioctahedral vermiculite-chlorite was indicated. Genesis of the studied asbestos rock is considered from the standpoint of high-temperature hydrothermal-metasomatic alteration of sediment by post-magmatic mineralized halide solutions.

Chemical composition of interstitial waters from sediments of brine-bearing deeps of the Red Sea

Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).