(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.

(Table 1) K-Ar age determinations on biotite from coarse sand within DSDP Sample 72-516F-76-4,107-115

Qualitative petrographic study of selected clastic horizons within the Eocene section of Hole 516F has revealed the presence of abundant fine-grained lithic fragments, probably volcanic, along with coarser fragments of quartz and feldspar apparently derived from a nearby plutonic terrain. In detail, poor sorting, presence of graded bedding, and an abundance of clay suggest these are turbidite horizons locally derived from a mixed volcanic/plutonic terrain, possibly with some direct contribution from contemporary volcanic ash falls. A progressive increase in plutonic versus volcanic components with time is, however, more consistent with an erosional origin for most of this material. Unusual euhedral dark biotite is abundant in several of the lower clastic horizons; it is most easily interpreted as microphenocrysts weathered in situ out of alkalic volcanic ash. Biotite separated from Sample 516F-76-4,107-115 cm, has been dated by the K-Ar method at about 46 Ma. Alkaline volcanoes active on the Rio Grande Rise in the middle Eocene would be the most probable source of this ash and would be consistent with other evidence for potassic, alkaline volcanism along the Rio Grande Rise and at the Tristan da Cunha hot spot.

(Table 1) Light minerals in sand at DSDP Leg 84 holes

The Middle America active continental margin is the best-sampled active plate margin to date, having been drilled during Legs 84, 67, and 66. With nine sites drilled on the continental slope of Guatemala and an additional site drilled on the Costa Rican slope, a summary of slope sediments and sedimentary processes can be made. Sediments are easily subdivided into a thick apron of Neogene and Quaternary volcanically derived hemipelagic and turbidite mud and mudstone and a thinner, more varied assemblage of mostly Paleogene mudstone, radiolarian mudstone, and limestone. This latter assemblage may contain hiatuses or be completely lacking between slope deposits and basement. Cores from the foot of the continental slope (Core 567A-19) consist of Campanian micrite. The pre-Neogene section is much thicker and of more terrigenous provenance beneath the forearc basin landward of the forearc structural high than on the continental slope. Sedimentary processes of the Neogene and Quaternary slope sediments include reworking of hemipelagic and turbidite deposits. Redeposition by slumping, plastic flow, and turbidity current-documentable through benthic foraminiferal analysis-occurs in intracanyon and canyon settings. Erosion by slumping and by turbidity current and deposition of mud or sand in canyons and in local depressions on the continental slope and different rates of sediment accumulation result in dramatic thickness variations of lithologic units over small distances in localized pockets of sand in small filled canyons on the slope or in sediment ponds, and in high-relief basement topography. The age of sediment overlying igneous basement ranges from Cretaceous to Quaternary. Gas hydrate was visible or inferred present at every site drilled during Leg 84. Nevertheless, except for a small amount in the last core, it was not recovered in sufficient quantities to be visible at Site 568, a site specifically chosen for the study of hydrate and located near Site 496, which was abandoned during Leg 67 because of the dangerous abundance of hydrates. The association of hydrate with porous, coarser sediment results in a distribution as localized and unpredictable as the slope sands off Guatemala, which do not occur in beds coherent enough to produce acoustic reflection. Although the normal lithologic section at Sites 567 and 496 limits the volume of sediment that could be part of an accretionary prism offshore Guatemala and the volume of sediment in the Trench axis is not sufficient to argue for significant accumulation of Cocos Plate sediments, the varied lithology and attenuated thickness of pre-Neogene sediment seaward of the forearc structural high do not exclude earlier accretion from the history of the Guatemalan continental margin.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Geochemistry of metasedimentary units of the Cambro-Ordovician Ross Orogen in North Victoria Land and Oates Land, Antarctica

Metasediments in the three early Palaeozoic Ross orogenic terranes in northern Victoria Land and Oates Land (Antarctica) are geochemically classified as immature litharenites to wackes and moderately mature shales. Highly mature lithotypes with Chemical Index of Weathering values of >=95 are typically absent. Geochemical and Rb-Sr and Sm-Nd isotope results indicate that the turbiditic metasediments of the Cambro-Ordovician Robertson Bay Group in the eastern Robertson Bay Terrane represent a very homogeneous series lacking significant compositional variations. Major variations are only found in chemical parameters which reflect differences in degree of chemical weathering of their protoliths and in mechanical sorting of the detritus. Geochemical data, 87Sr/ 86Sr t=490 Ma ratios of 0.7120 - 0.7174, epsilonNd, t=490 Ma values of -7.6 to -10.3 and single-stage Nd-model ages of 1.7 - 1.9 Ga are indicative of an origin from a chemically evolved crustal source of on average late Palaeoproterozoic formation age. There is no evidence for significant sedimentary infill from primitive "ophiolitic" sources. Metasediments of the Middle Cambrian Molar Formation (Bowers Terrane) are compositionally strongly heterogeneous. Their major and trace element data and Sm-Nd isotope data (epsilonNd, t=500 Ma values of -14.3 to -1.2 and single-stage Nd-model ages of 1.7 - 2.1 Ga) can be explained by mixing of sedimentary input from an evolved crustal source of at least early Palaeoproterozoic formation age and from a primitive basaltic source. The chemical heterogeneity of metasediments from the Wilson Terrane is largely inherited from compositional variations of their precursor rocks as indicated by the Ni vs TiO2 diagram. Single-stage Nd-model ages of 1.6 -2.2 Ga for samples from more western inboard areas of the Wilson Terrane (epsilonNd, t=510 Ma -7.0 to -14.3) indicate a relatively high proportion of material derived from a crustal source with on average early Palaeoproterozoic formation age. Metasedimentary series in an eastern, more outboard position (epsilonNd, t=510 Ma -5.4 to -10.0; single-stage Nd model ages 1.4 - 1.9) on the contrary document stronger influence of a more primitive source with younger formation ages. The chemical and isotopic characteristics of metasediments from the Bowers and Wilson terranes can be explained by variable contributions from two contrasting sources: a cratonic continental crust similar to the Antarctic Shield exposed in Georg V Land and Terre Adélie some hundred kilometers west of the study area and a primitive basaltic source probably represented by the Cambrian island-arc of the Bowers Terrane. While the data for metasediments of the Robertson Bay Terrane are also compatible with an origin from an Antarctic-Shield-type source, there is no direct evidence from their geochemistry or isotope geochemistry for an island-arc component in these series.

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

(Table 1) Water-extractable and acid-extractable carbohydrates in DSDP Leg 65 samples

Selected parts of ten frozen core samples from Holes 482A, 482B, 483A, and 485A, Leg 65 of the Deep Sea Drilling Project (DSDP), were analyzed for residual carbohydrates in order to determine the provenance and history of the organic material in the sediments. The samples, which represented silty-clay, shale, and nannofossil- chalk sediments, were analyzed for water-soluble monosaccharides, acid-soluble monosaccharides, and for starch and cellulose. Most samples yielded positive results for acid-extractable (polymeric) arabinose, fucose, xylose, mannose, galactose, and glucose. Amylose was detected in seven of the samples, whereas cellulose was found in only one. Possible explanations for the relatively high levels of free sugars are suggested in the conclusions to this chapter.