Nd, Sr and Pb isotopic composition of eolian dust deposited in the central North Pacific

The silicate fractions of recent pelagic sediments in the central north Pacific Ocean are dominated by eolian dust derived from central Asia. An 11 Myr sedimentary record at ODP Sites 885/886 at 44.7°N, 168.3°W allows the evaluation of how such dust and its sources have changed in response to late Cenozoic climate and tectonics. The extracted eolian fraction contains variable amounts (>70%) of clay minerals with subordinate quartz and plagioclase. Uniform Nd isotopic compositions (epsilon-Nd =38.6 to 310.5) and Sm/Nd ratios (0.170-0.192) for most of the 11 Myr record demonstrate a well-mixed provenance in the basins north of the Tibetan Plateau and the Gobi Desert that was a source of dust long before the oldest preserved Asian loess formed. epsilon-Nd values of up to 36.5 for samples 62.9 Ma indicate <=35 wt% admixture of a young, Kamchatka-like volcanic arc component. The coherence of Pb and Nd in the erosional cycle allows us to constrain the Pb isotopic composition of Asian loess devoid of anthropogenic contamination to 206Pb/204Pb =18.97 +/- 0.06, 207Pb/204Pb =15.67 +/- 0.02, 208Pb/204Pb =39.19 +/- 0.11. 87Sr/86Sr (0.711-0.721) and Rb/Sr ratios (0.39-1.1) vary with dust mineralogy and provide an age indication of ~250 Ma. 40Ar/39Ar ages of six dust samples are uniform around 200 Ma and match the K-Ar ages of modern dust deposited on Hawaii. These data reflect the weighted age average of illite formation. Changes from illite- smectite with significant kaolinite to illite- and chlorite-rich, kaolinite-free assemblages since the late Pliocene document changes in the intensity of chemical weathering in the source region. Such weathering evidently did not disturb the K-Ar systematics, and only induced scatter in the Rb-Sr data. We propose that when smectite forms at the expense of illite, K and Ar are quantitatively lost from what becomes smectite, but are quantitatively retained in adjacent illite layers. 40Ar/39Ar age data, therefore, are insensitive to smectite formation during chemical weathering but date the diagenetic growth of illite, the major K-bearing phase in the dust. Over the past 12 Myr, the dust flux to the north Pacific increased by more than an order of magnitude, documenting a substantial drying of central Asia. This climatic change, however, did not alter the ultimate source of the dust, and neoformational products of chemical weathering always remained subordinate to assemblages reworked by mechanical erosion in dust deposited in eastern Asia and the Pacific Ocean.

Grain size distribution and clay mineralogy of upper Miocene sediments of ODP Hole 107-652A

The upper Miocene sedimentary sequence of Site 652, located on the lower continental margin of eastern Sardinia, was cored and logged during Ocean Drilling Program (ODP) Leg 107. Geophysical and geochemical logs from the interval 170-365 m below seafloor (mbsf), as well as various core measurements (CaCO3, grain size, X-ray diffraction), provide a mineralogical-geochemical picture that is interpreted in the framework of the climatic and tectonic evolution of the western Tyrrhenian. The results indicate the presence of short- and long-term mineralogical variations. Short-term variations are represented by calcium-carbonate fluctuations in which the amount of CaCO3 is correlated to the grain size of the sediments; coarser sediments are associated with high carbonate content and abundant detrital material. Long-term variation corresponds to a gross grain-size change in the upper part of the sequence, where predominantly fine-grained sediments may indicate a gradual deepening of the lacustrine basin towards the Pliocene. Regional climatic changes and rift-related tectonism are possible causes of this variability in the sedimentation patterns. The clay association is characterized by chlorite, illite, and smectite as dominant minerals, as well as mixed-layers clays, kaolinite, and palygorskite. Chlorite, mixed-layers clays, and illite increase at the expense of smectite below the pebble zone (335 mbsf). This is indicative of diagenetic processes related to the high geothermal gradient and to the chemistry of the evaporative pore waters, rather than to changes in the depositional environment.

Holocene Mg/Ca, alkenones, and light stable isotope measurements on the outer North Iceland shelf, sediment core MD99-2269

We present new Holocene century to millennial-scale proxies for the well-dated piston core MD99-2269 from Húnaflóadjúp on the North Iceland Shelf. The core is located in 365 mwd and lies close to the fluctuating boundary between Atlantic and Arctic/Polar waters. The proxies are: alkenone-based SST°C, and Mg/Ca SST°C estimates and stable d13C and d18O values on planktonic and benthic foraminifera. The data were converted to 60 yr equi-spaced time-series. Significant trends in the data were extracted using Singular Spectrum Analysis and these accounted for between 50% and 70% of the variance. A comparison between these data with previously published climate proxies from MD99-2269 was carried out on a data set which consisted of 14-variable data set covering the interval 400-9200 cal yr BP at 100 yr time steps. This analysis indicated that the 1st two PC axes accounted for 57% of the variability with high loadings clustering primarily into "nutrient" and "temperature" proxies. Clustering on the 100 yr time-series indicated major changes in environment at ~6350 and ~3450 cal yr BP, which define early, mid- and late Holocene climatic intervals. We argue that a pervasive freshwater cap during the early Holocene resulted in warm SST°s, a stratified water column, and a depleted nutrient supply. The loss of the freshwater layer in the mid-Holocene resulted in high carbonate production, and the late Holocene/neoglacial interval was marked by significantly more variable sea surface conditions.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

(Table 1) Results of X-ray radiographic analyses of authigenic phosphorites from the Southwest Africa shelf

In the biologically productive area on the Southwest Africa shelf a current process of diagenetic phosphorite formation occurs. Remains of phytoplankton are the main source of phosphorus in host bottom sediments. Phosphorus concentrates in nodules due to its redistribution in bottom sediments and precipitation from interstitial waters. Accumulation of the phosphate nodules, as well as of scattered fish bone debris in sediments occurs at sudden change in hydrological conditions and removal of fine sediment fractions due to increased bottom currents or during transgressions.

Paleomagnetic and rock magnetic properties of ODP Leg 173 sites, west Iberia continental margin

We present detailed paleomagnetic and rock magnetic results of rock samples recovered during Leg 173. The Leg 173 cores display a multicomponent magnetization nature. Variations in magnetic properties correlate with changes in lithology that result from differences in the abundance and size of magnetic minerals. The combined investigation suggests that the magnetic properties of the "fresher" peridotite samples from Site 1070 are controlled mainly by titanomagnetite, with a strong Verwey transition in the vicinity of 110 K, and with field- and frequency-dependent susceptibility curves that resemble those of titanomagnetites. These results are in excellent agreement with thermomagnetic characteristics where titanomagnetites with Curie temperature ~580°C were identified from the "fresher" peridotites. In contrast to the magnetic properties observed from the "fresher" peridotites, the low-temperature curves for the "altered" peridotites did not show any Verwey transition. Thermomagnetic analysis using the high-temperature vibrating sample magnetometer also failed to show evidence for titanomagnetites. The remanent magnetization is carried by a thermally unstable mineral that breaks down at ~420°C, probably maghemite. The field- and frequency-dependent relationships are also directly opposite to those in the reversal zone, with no signs of titanomagnetite characteristics. Altogether, these rock magnetic data seem to be sensitive indicators of alteration and support the contention that maghemite is responsible for the magnetic signatures displayed in the altered peridotites of the upper section. The magnetic minerals of the basement rocks from Sites 1068, 1069, and 1070 are of variable particle size but fall within the pseudo-single-domain size range (0.2-14 µm). The average natural remanent magnetization (NRM) intensity of recovered serpenitinized peridotite is typically on the order of 20 mA/m for samples from Site 1068, but ~120 mA/m for samples from Site 1070. The much stronger magnetization intensity of Site 1070 is apparently in excellent agreement with the observed magnetic anomaly high. Nearly half of the NRM intensity remained after 400°C demagnetization, suggesting that the remanence can contribute significantly to the marine magnetic anomaly.

Rock magnetic properties of ODP Leg 134 sites

During Leg 134, the influence of ridge collision and subduction on the structural evolution of island arcs was investigated by drilling at a series of sites in the collision zone between the d'Entrecasteaux Zone (DEZ) and the central New Hebrides Island Arc. The DEZ is an arcuate Eocene-Oligocene submarine volcanic chain that extends from the northern New Caledonia Ridge to the New Hebrides Trench. High magnetic susceptibilities and intensities of magnetic remanence were measured in volcanic silts, sands, siltstones, and sandstones from collision zone sites. This chapter presents the preliminary results of studies of magnetic mineralogy, magnetic properties, and magnetic fabric of sediments and rocks from Sites 827 through 830 in the collision zone. The dominant carrier of remanence in the highly magnetic sediments and sedimentary rocks in the DEZ is low-titanium titanomagnetite of variable particle size. Changes in rock magnetic properties reflect variations in the abundance and size of titanomagnetite particles, which result from differences in volcanogenic contribution and the presence or absence of graded beds. Although the anisotropy of magnetic susceptibility results are difficult to interpret in terms of regional stresses because the cores were azimuthally unoriented, the shapes of the susceptibility ellipsoids provide information about deformation style. The magnetic fabric of most samples is oblate, dominated by foliation, as is the structural fabric. The variability of degree of anisotropy (P) and a factor that measures the shape of the ellipsoid (q) reflect the patchy nature of deformation, at a micrometer scale, that is elucidated by scanning electron microscope analysis. The nature of this patchiness implies that deformation in the shear zones is accomplished primarily by motion along bedding planes, whereas the material within the beds themselves remains relatively undeformed.

Chemical composition of oxide-phosphorite pavement from the Blake Plateau under various preparation treatment

Sample preparation technique is critical for valid chemical analyses. A main source of error comes from the fact that the great specific surface area of crusts or nodules enhances their tendency to retain or attract hygroscopic moisture. Variable treatment of this moisture can in extreme cases lead to analytical value differences as great as 40-50 %. In order to quantify these influences, samples of ferromanganese oxide-phosphorite pavement from the Blake Plateau have been subjected to various drying techniques before analysis using X-ray fluorescence.