(Table 1) Mass-accumulation rates for the non-authigenic, inorganic, crystalline, eolian component of sediments recovered at DSDP Hole 62-463

Elevated regions in the central parts of ocean basins are excellent for study of accumulation of eolian material. The mass-accumulation rates of this sediment component appear to reflect changes in the influx of volcanic materials through the Early Cretaceous to Recent history of Deep Sea Drilling Project Site 463, on the Mid-Pacific Mountains. Four distinct episodes of eolian accumulation occurred during the Cretaceous: two periods of moderate accumulation, averaging about 0.2 to 0.3 g/cm**2/10**3 yr, 67 to 70.5 m.y. ago and 91 to 108 m.y. ago; a period of low accumulation, approximately 0.03 g/cm**2/10**3 yr, 70.5 to 90 m.y. ago; and a period of high accumulation, about 0.9 g/cm**2/10**3 yr, 109 to 117 m.y. ago (bottom of the hole). Much of the Cenozoic section is missing from Site 463. Upper Miocene to Recent sediments record an upward increase in accumulation rates, from less than 0.01 to about 0.044 g/cm**2/10**3 yr. The late Pliocene-Pleistocene peak may reflect the change to glacial-wind regimes, as well as an increase in volcanic source materials.

(Table 2) Oxygen isotope composition of authigenic and detrital phosphates from ODL Leg 201 sites

Many (bio)geochemical processes that bring about changes in sediment chemistry normally begin at the sediment-water interface, continue at depth within the sediment column and may persist throughout the lifetime of sediments. Because of the differential reactivity of sedimentary phosphate phases in response to diagenesis, dissolution/precipitation and biological cycling, the oxygen isotope ratios of phosphate (d18OP) can carry a distinct signature of these processes, as well as inform on the origin of specific P phases. Here, we present results of sequential sediment extraction (SEDEX) analyses combined with d18OP measurements, aimed at characterizing authigenic and detrital phosphate phases in continental margin sediments from three sites (Sites 1227, 1228 and 1229) along the Peru Margin collected during ODP Leg 201. Our results show that the amount of P in different reservoirs varies significantly in the upper 50 m of the sediment column, but with a consistent pattern, for example, detrital P is highest in siliciclastic-rich layers. The d18OP values of authigenic phosphate vary between 20.2 per mil and 24.8 per mil and can be classified into at least two major groups: authigenic phosphate precipitated at/near the sediment-water interface in equilibrium with paleo-water oxygen isotope ratios (d18Ow) and temperature, and phosphate derived from hydrolysis of organic matter (Porg) with subsequent incomplete to complete re-equlibration and precipitated deeper in the sediments column. The d18OP values of detrital phosphate, which vary from 7.7-15.4 per mil, suggest two possible terrigenous sources and their mixtures in different proportions: phosphate from igneous/metamorphic rocks and phosphate precipitated in source regions in equilibrium with d18Ow of meteoric water. More importantly, original isotopic compositions of at least one phase of authigenic phosphates and all detrital phosphates are not altered by diagenesis and other biogeochemical changes within the sediment column. These findings help to understand the origin and provenance of P phases and paleoenvironmental conditions at/near the sediment-water interface, and to infer post-depositional activities within the sediment column.

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

(Table 2) Terrigenous, authigenic and biogenic composition of sediments at DSDP Hole 93-603B

Pelagic sedimentation during the Early Cretaceous at Site 603 produced alternations of laminated marly limestone and bioturbated limestone-a facies typical of the "Blake-Bahama Formation" of the western Atlantic. This limestone is a nannofossil micrite, rich in calcified radiolarians, with variable amounts of organic matter, pyritized radiolarian tests, fish debris, and micaceous silt. The laminated marly limestone layers are enriched in organic matter when compared with the intervals of bioturbated limestone. The organic carbon is predominantly terrestrial plant debris; where the organic-carbon content is in excess of 1%, there is also a significant marine-derived component. Laminations can result either from bands of alternately enriched and depleted opaque material and clay, or from bands of elongate lenses (microflasers) of micrite, which could be plastically deformed pellets or diagenetic features. The alternating intervals of laminated and bioturbated structures may have resulted from combined changes in surface productivity, in the influx of terrigenous organic matter, and in the intensity of bottom circulation, which led to episodic oxygen depletion in the bottom water and sediments. Variations in the relative proportions of laminated clay-rich and bioturbated lime-rich limestone and in the development of cycles between these structures make it possible to subdivide the Lower Cretaceous pelagic facies into several subunits which appear to be regional in extent. Bioturbated limestone is dominant in the Berriasian, laminated marly limestone in the Valanginian and Barremian-lower Aptian, and well-developed alternations between these end members in the Hauterivian. The Hauterivian to lower Aptian sediments contain abundant terrigenous clastic turbidites associated with a submarine fan complex. These changes in the general characteristics of the pelagic sediment component of the Blake-Bahama Formation at Site 603 are synchronous with those in the Blake-Bahama Basin (Sites 534 and 391) to the south. Carbonate sedimentation ended in the early Aptian, probably because of a regional shoaling of the carbonate compensation depth.

Discriminating stromatolite formation modes using rare earth element geochemistry: Trapping and binding versus in situ precipitation of stromatolites from the Neoproterozoic Bitter Springs Formation, Northern Territory, Australia

Stromatolites consist primarily of trapped and bound ambient sediment and/or authigenic mineral precipitates, but discrimination of the two constituents is difficult where stromatolites have a fine texture. We used laser ablation-inductively coupled plasma-mass spectrometry to measure trace element (rare earth element – REE, Y and Th) concentrations in both stromatolites (domical and branched) and closely associated particulate carbonate sediment in interspaces (spaces between columns or branches) from bioherms within the Neoproterozoic Bitter Springs Formation, central Australia. Our high resolution sampling allows discrimination of shale-normalised REE patterns between carbonate in stromatolites and immediately adjacent, fine-grained ambient particulate carbonate sediment from interspaces. Whereas all samples show similar negative La and Ce anomalies, positive Gd anomalies and chondritic Y/Ho ratios, the stromatolites and non-stromatolite sediment are distinguishable on the basis of consistently elevated light REEs (LREEs) in the stromatolitic laminae and relatively depleted LREEs in the particulate sediment samples. Additionally, concentrations of the lithophile element Th are higher in ambient sediment samples than in stromatolites, consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites. These findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment. Hence, high resolution trace element (REE + Y, Th) geochemistry can discriminate fine-grained carbonates in these stromatolites from coeval non-stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation, presumably within microbial mats/biofilms, rather than by trapping and binding of ambient sediment. Identification of the source of fine carbonate in stromatolites is significant, because if it is not too heavily contaminated by trapped ambient sediment, it may contain geochemical biosignatures and/or direct evidence of the local water chemistry in which the precipitates formed.

The verdine facies off French Guiana

This chapter reviews green grains from the shelf of French Guiana as a regional example of sedimentologic process occurring on the whole stable continental margin from the Amazon to the Orinoco River. Green grains have been observed and analyzed off the Orinoco delta and on the continental shelf of Surinam. These green grains were identified as “chamosite” and “glauconite.” The muddy coast of French Guiana is generally very flat and occupied by wet swamps and mangrove as a result of the equatorial climate. Most green grains on the continental shelf represent the verdine facies. Green grains are ubiquitous on the shelf and top of the slope off French Guiana. Two sedimentological facies exist: glaucony deeper than 150 m and verdine at shallower depths. The verdine facies has mainly developed from mineral debris and especially chloritized biotite. Carbonate bioclasts and faecal pellets are also utilized. The mica flakes were never wholly replaced by authigenic clay and the phenomenon leads to mixed grains where authigenic and substrate remains are recognizable. Carbonate substrates lead to mainly clay pure green grains becasue the initial carbonate has been dissolved. The formation of verdine can be located in a general marine environment at a comparatively warm sea-water temperature and at a depth probably shallower than 60 m.

Imaging fluid solid interactions in hydrocarbon reservoir rocks

The environmental scanning electron microscope (ESEM) has been used to image liquid hydrocarbons in sandstones and oil shales. Additionally, the fluid sensitivity of selected clay minerals in hydrocarbon reservoirs was assessed via three case studies: HCl acid sensitivity of authigenic chlorite in sandstone reservoirs, freshwater sensitivity of authigenic illite/smectite in sandstone reservoirs, and bleach sensitivity of a volcanic reservoir containing abundant secondary chlorite/corrensite. The results showed the suitability of using ESEM for imaging liquid hydrocarbon films in hydrocarbon reservoirs and the importance of simulating in situ fluid-rock interactions for hydrocarbon production programmes. In each case, results of the ESEM studies greatly enhanced prediction of reservoir/borehole reactions and, in some cases, contradicted conventional wisdom regarding the outcome of potential engineering solutions. (C) 1993 Wiley-Liss, Inc.