Calcium carbonate, sedimentation and mass accumulation rates at DSDP Site 85-572

At Site 572, located at 1°N, 114° W (3903 m water depth), we recovered a continuous hydraulic piston cored section of upper Miocene to upper Pleistocene pelagic sediments. The sediment is composed of biogenic carbonate and silica with nonbiogenic material as a minor component. Detailed analysis of the calcium carbonate content shows that the degree of variability in carbonate deposition apparently changed markedly between the late Miocene and Pliocene at this equatorial Pacific site. During this interval carbonate mass accumulation rates decreased from 2.6 to 0.8 g/cm**2 per 10**3 yr. If we assume that variations in CaCO3 content reflect changes in the degree of dissolution, then the detailed carbonate analysis would suggest that the degree of variability in carbonate deposition decreases by a factor of 5 as the dominant wavelength of variations increases significantly. However, if the variability in carbonate concentration is described in terms of changes in mean mass accumulation, calculations then suggest that relatively small changes in noncarbonate rates may be important in controlling the observed carbonate records. In addition, the analysis suggests that the degree of variability observed in pelagic carbonate data may in part reflect total accumulation rates. Intervals with high sedimentation rates show lower amplitude variations in concentration than intervals with lower sedimentation rates for the same degree of change in the carbonate accumulation rate.

Magnetic properties, grain sizes and minerals at DSDP Site 83-504B

Twenty-seven samples from the Leg 83 section of Hole 504B have been investigated using magnetic, optical, and electron optical methods. The primary magnetic mineral to crystallize was titanomagnetite of approximate composition Fe2.4Ti0.6O4 (TM60), but none survives, nor is there evidence of titanomaghemite produced by oxidation of TM60. The average measured magnetic properties can be interpreted in terms of magnetite, Fe3O4, having average grain size of <1 µm and present in average volume concentration of - 0.5%. The intensity of the natural remanent magnetization (NRM) of the rocks could also be accounted for as being a thermoremanence carried by this mineral. Although the heterogeneity of the titanomagnetite grains could be detected optically, the texture of the intergrown phases is poorly developed. In some samples from the massive units of the lower part of the section, trellis patterns were visible. The Fe3O4 present in the intergrowths is too intimately mixed with the other intergrown phases to be revealed by electron microprobe analysis that simply returns the bulk composition of the intergrowth (oxidized TM60). The path by which the mineral assemblage evolved from TM60 to an Fe304-containing intergrowth, under the temperature and pressure conditions obtaining in the Leg 83 section, makes interesting speculation. Deuteric oxidation, maghemitization/inversion, or some hypothetical low-temperature/high-pressure oxidation by a leaching-of-iron process may all play roles.

Isotopic and chemical compositions of rocks and minerals from the TAG hydrothermal mound, ODP Site 957

Strontium- and oxygen-isotopic measurements of samples recovered from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound during Leg 158 of the Ocean Drilling Program provide important constraints on the nature of fluid-rock interactions during basalt alteration and mineralization within an active hydrothermal deposit. Fresh Mid-Ocean Ridge Basalt (MORB), with a 87Sr/86Sr of 0.7026, from the basement beneath the TAG mound was altered at both low and high temperatures by seawater and altered at high temperature by near end-member black smoker fluids. Pillow breccias occurring beneath the margins of the mound are locally recrystallized to chlorite by interaction with large volumes of conductively heated seawater (>200°C). The development of a silicified, sulfide-mineralized stockwork within the basaltic basement follows a simple paragenetic sequence of chloritization followed by mineralization and the development of a quartz+pyrite+paragonite stockwork cut by quartz-pyrite veins. Initial alteration involved the development of chloritic alteration halos around basalt clasts by reaction with a Mg-bearing mixture of upwelling, high-temperature (>300°C), black smoker-type fluid with a minor (<10%) proportion of seawater. Continued high-temperature (>300°C) interaction between the wallrock and these Mg-bearing fluids results in the complete recrystallization of the wallrock to chlorite+quartz+pyrite. The quartz+pyrite+paragonite assemblage replaces the chloritized basalts, and developed by reaction at 250-360°C with end-member hydrothermal fluids having 87Sr/86Sr ~0.7038, similar to present-day vent fluids. The uniformity of the 87Sr/86Sr ratios of hydrothermal assemblages throughout the mound and stockwork requires that the 87Sr/86Sr ratio of end-member hydrothermal fluids has remained relatively constant for a time period longer than that required to change the interior thermal structure and plumbing network of the mound and underlying stockwork. Precipitation of anhydrite in breccias and as late-stage veins throughout most of the mound and stockwork, down to at least 125 mbsf, records extensive entrainment of seawater into the hydrothermal deposit. 87Sr/86Sr ratios indicate that most of the anhydrite formed from ~2:1 mixture of seawater and black smoker fluids (65%±15% seawater). Oxygen-isotopic compositions imply that anhydrite precipitated at temperatures between 147°C and 270°C and require that seawater was conductively heated to between 100°C and 180°C before mixing and precipitation occurred. Anhydrite from the TAG mound has a Sr-Ca partition coefficient Kd ~0.60±0.28 (2 sigma). This value is in agreement with the range of experimentally determined partition coefficients (Kd ~0.27-0.73) and is similar to those calculated for anhydrite from active black smoker chimneys from 21°N on the East Pacific Rise. The d18O (for SO4) of TAG anhydrite brackets the value of seawater sulfate oxygen (~9.5?). Dissolution of anhydrite back into the oceans during episodes of hydrothermal quiescence provides a mechanism of buffering seawater sulfate oxygen to an isotopically light composition, in addition to the precipitation and dissolution of anhydrite within the oceanic basement during hydrothermal recharge at the mid-ocean ridges.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Late Pliocene carbonate mineralogy of ODP Hole 133-818B

Shedding of shallow carbonate material toward the deep slopes and basin floors is clearly tied to the position of the carbonate bank tops relative to the photic zone. The onset of bank shedding in periplatform sediments can record either the flooding of the bank tops within the photic zone during a rise in sea level following a period of exposure, referred to in the literature as the "highstand shedding" scenario, or the reentry of the bank tops into the photic zone during a lowering of sea level following a period of drowning, referred to as the "lowstand shedding" scenario. Results from Leg 133 post-cruise research on the Pliocene sequences, drilled in six sites within different slope settings of the Queensland Plateau, seem to point out that the latter "lowstand shedding" scenario can be applied to this particular carbonate system. At the Queensland Plateau sites, the early Pliocene (5.2-3.5 Ma) and the earliest part of the late Pliocene (3.5-2.9 Ma) age sequences were characterized, especially in the ôdeepö Sites 811 and 817, by pelagic sediments (foraminifers and coccoliths) and by typically pelagic sedimentation rates not exceeding 20 mm/k.y. The earliest part of the late Pliocene age section was characterized by well-developed hardgrounds in the "shallow" Sites 812 and 814 and by normal pelagic sediments mixed with reworked phosphatized planktonic foraminifers in Site 813. Finally, the early part of the late Pliocene (2.9-2.4 Ma) section was characterized by high sedimentation rates, related to the shedding and admixture into the pelagic sediments of bank-derived materials. These bank-derived materials consist of either diagenetically unaltered fine aragonite with traces of dolomite in Site 818 or micritic calcite resulting from seafloor and/or shallow burial alteration in the deepest Sites 817 and 811. The highest sedimentation rates (163 mm/k.y.) were recorded in Site 818, drilled nearest the modern carbonate bank of Tregrosse Reef. The sedimentation rates decrease with increasing distance from Tregrosse Reef - 120 mm/k.y. in Site 817 and 47.5 mm/k.y. in Site 811. The initial appearance of fine aragonite in Site 818, corresponding to the transition from pelagic to periplatform sedimentation rates, has been dated at 2.9 Ma. This Pliocene sediment pattern on the Queensland Plateau is different from the pattern observed in sediments from two earlier ODP legs (i.e., Leg 101 in the Bahamas and in Leg 115 in the Maldives), where aragonite-rich sediments, characterized by high periplatform sedimentation rates, were observed in the lower Pliocene section (5.2-3.5 Ma), whereas the upper Pliocene (3.5-1.6 Ma) sediments are more pelagic in nature and are characterized by low sedimentation rates or major hiatuses. These Pliocene periplatform sequences in the Bahamas and in the Maldives and late Quaternary age periplatform sequences worldwide have pointed out that "highstand shedding" was the typical response of carbonate platforms to fluctuations in sea level, just opposite to a "lowstand shedding" response to sea-level fluctuations, typical of siliciclastic shelves. Assuming that the envelope of Haq et al.'s (1987) sea-level curve, showing a well-defined lowering of sea level between 3.5 and 2.9 Ma, can also be applied to the southwest Pacific Ocean, based on a high-resolution Pliocene d18O record from the Ontong Java Plateau recently published by Jansen et al. (1993, doi:10.2973/odp.proc.sr.130.028.1993), the Pliocene periplatform sequences on the Queensland Plateau would have recorded the reentry of the bank tops into the photic zone during a general lowering of sea level, following an interval characterized by high sea level, during which the shallow carbonate system on the Queensland Plateau was drowned. The early Pliocene age (5.2-3.5 Ma) sediments deposited on the Queensland Plateau, an established interval of eustatic sea-level highstand, are typically pelagic in character. In addition, relatively cold surface temperatures (estimated to have ranged from 18° to 20°C by Isern et al. [this volume]) might have also stressed the reefs during early Pliocene time and contributed to the drowning of the Queensland Plateau carbonate system during the late Miocene and early Pliocene. Differential and relatively high subsidence rates, inferred by variations in paleodepth of water (based upon benthic foraminifer assemblages; Katz and Miller, this volume) may also have influenced the drowning of the carbonate bank tops on the Queensland Plateau during the late Miocene and early Pliocene. The sediments of early late Pliocene age (2.9-2.4 Ma), a well-established interval of lowering of sea level, are clearly periplatform and cyclic in nature. High-frequency (~40 k.y.) aragonite cycles, well-developed between 2.9 and 2.45 Ma, correlate with the planktonic high-resolution Pliocene d18O record from the Ontong Java Plateau, a good sea-level proxy (Jansen et al., in press). Contrary to late Quaternary age aragonite cycles from the Bahamas, the Nicaragua Rise, the Maldives, and the Queensland Plateau, the late Pliocene aragonite cycles in Hole 818B display high levels of aragonite during glacial stages and, therefore, lowstands of sea level. In addition, sediments deposited during the earliest part of the late Pliocene (3.5-2.9 Ma), transition between the early Pliocene highstand and the late Pliocene lowering in sea level, have recorded the first evidence of a fall in sea level, by (1) the occurrence of synchronous submarine hardgrounds in the two shallowest sites (Sites 812 and 814), (2) the deposition of reworked material from the shallower part of the slope into the intermediate Sites 813 and 818, and (3) the deposition of pelagic sediments in the deepest Sites 817 and 817. In summary, contrary to previous findings, the Pliocene periplatform sediments on the Queensland Plateau appear to have recorded a regional shedding of shallow carbonate bank tops during an interval of sea-level lowering, a good illustration of the "carbonate lowstand shedding" scenario, occurring during the reentry of previously drowned carbonate bank tops into the photic zone related to a decrease in sea level.

Pliocene-Plistocene deposition of carbonate and organic carbon in ODP Hole 159-959C

During Ocean Drilling Program (ODP) Leg 159, four sites (Sites 959-962) were drilled along a depth transect on the Côte d'Ivoire/Ghana Transform Margin. In this study, the Pliocene-Pleistocene history of carbonate and organic carbon accumulation at Hole 959C is reconstructed for the eastern equatorial Atlantic off the Ivory Coast/Ghana based on bulk carbonate, sand fraction, organic carbon, and other organic geochemical records (d13Corg, marine organic matter percentages derived from organic petrology, hydrogen index, C/N). Pliocene-Pleistocene sedimentation off the Ivory Coast/Ghana was strongly affected by low mean sedimentation rates, which are attributed to persistently enhanced bottom-water velocities related to the steep topography of the transform margin. Sand fraction and bulk carbonate records reveal typical glacial/interglacial cycles, preserved, however, with low time resolution. Intermediate carbonate accumulation rates observed throughout the Pliocene-Pleistocene suggest intense winnowing and sediment redistribution superimposed by terrigenous dilution. 'Atlantic-type' sand and carbonate cycles, consistent with records from pelagic areas of the eastern equatorial Atlantic, are encountered at Hole 959C prior to about 0.9 Ma. Total organic carbon (TOC) records are frequently inversely correlated to carbonate contents, indicating mainly productivity-driven carbonate dissolution related to changes in paleoproductivity. During Stages 22-24, 20, 16, 12, 8, and 4, sand and carbonate records reveal a 'Pacific-type' pattern, showing elevated contents during glacials commonly in conjunction with enhanced TOC records. Formation of 'Pacific-type' patterns off the Ivory Coast/Ghana is attributed to drastically increased bottom-water intensities along the transform margin in accordance with results reported from the Walvis Ridge area. Short-term glacial/interglacial changes in paleoproductivity off the Ivory Coast/Ghana are to some extend recognizable during glacials prior to 1.7 Ma and interglacial Stages 21, 19, 13, 9, and 1. Enhanced coastal upwelling during interglacials is attributed to local paleoclimatic and oceanographic conditions off the Ivory Coast/Ghana. Quantitative estimates of marine organic carbon based on organic petrologic and d13Corg records reveal an offset in concentration ranging from 15% to 60%. Highest variabilities of both records are recorded since ~0.9 Ma. Discrepancies between the isotopic and microscopic records are attributed to an admixture of C4 plant debris approaching the eastern equatorial Atlantic via atmospheric dust. Terrestrial organic material likely originated from the grass-savannah-covered Sahel zone in central Africa. Estimated C4 plant concentrations and accumulation rates range from 10% to 37% and from almost zero to 0.006 g/cm**2/k.y., respectively. The strongest eolian supply to the northern Gulf of Guinea is indicated between 1.9 and 1.68 Ma and during glacial isotopic Stages 22-24, 20, 14, and 12. The presence of grass-type plant debris is further supported by organic petrologic studies, which reveal well-preserved cell tissues of vascular plants or tube-shaped, elongated terrestrial macerals showing different levels of oxidation.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Carbonate and Aluminium accumulation in the central equatorial Pacific Ocean

We examined the flux of Al to sediment accumulating beneath the zone of elevated productivity in the central equatorial Pacific Ocean, along a surface sediment transect at 135°W as well as downcore for a 650 kyr record at 1.3°N, 133.6°W. Across the surface transect, a pronounced, broadly equatorially symmetric increase in Al accumulation is observed, relative to Ti, with Al/Ti ratios reaching values 3-4 times that of potential detrital sources. The profile parallels biogenic accumulation and the modeled flux of particulate 234Th, suggesting rapid and preferential adsorptive removal of Al from seawater by settling biogenic particles. Normative calculations confirm that most Al is unsupported by the terrigenous fraction. The observed distributions are consistent with previous observations of the relative and absolute behavior of Al and Ti in seawater, and we can construct a reasonable mass balance between the amount of seawater-sourced Al retained in the sediment and the amount of seawater Al available in the overlying column. The close tie between Al/Ti and biogenic accumulation (as opposed to concentration) emphasizes that biogenic sedimentary Al/Ti responds to removal-transport phenomena and not bulk sediment composition. Thus, in these sediments dominated by the biogenic component, the bulk Al/Ti ratio reflects biogenic particle flux, and by extension, productivity of the overlying seawater. The downcore profile of Al/Ti at 1.3°N displays marked increases during glacial episodes, similar to that observed across the surface transect, from a background value near Al/Ti of average upper crust. The excursions in Al/Ti are stratigraphically coincident with maxima in both bulk and CaCO3 accumulation and the excess Al appears to not be preferentially affiliated with opaline or organic phases. Consistent with the similar behavioral removal of Al and 234Th, the latter of which responds to the total particle flux, the Al flux reflects carbonate accumulation only because carbonate comprises the dominant flux in these particular deposits. These results collectively indicate that (1) Al in biogenic sediment and settling biogenic particles is strongly affected by a component adsorbed from seawater. Therefore, the common tenet that Al is dominantly associated with terrestrial particulate matter, and the subsequent use of Al distributions to calculate the abundance and flux of terrestrial material in settling particles and sediment, needs to be reevaluated. (2) The Al/Ti ratio in biogenic sediment can be used to trace the productivity of the overlying water, providing a powerful new paleochemical tool to investigate oceanic response to climatic variation. (3) The close correlation between the Al/Ti productivity signal and carbonate maxima downcore at 1.3°N suggests that the sedimentary carbonate maxima in the central equatorial Pacific Ocean record increased productivity during glacial episodes.

Carbonate and bulk grain-size record for ODP Leg 130 holes

A major goal of Ocean Drilling Program (ODP) Leg 130 was to drill four sites down the northeastern flank of the Ontong Java Plateau to collect a series of continuous sedimentary sequences that would provide a depth transect of Neogene sediments. In particular, the study of the sediments recovered along the depth transect is expected to yield high-resolution stratigraphic, geochemical, and physical properties records across intervals of major paleoceanographic changes by evaluating variations of primary sedimentological and paleoceanographic indicators (e.g., carbonates, isotopes, grain size, microfossil assemblages, etc.). This data report presents the results of highresolution (3-5 Ka sample intervals) analyses of carbonate concentration and bulk sediment grain size at Sites 803-806 for the time interval from 2 Ma to the present.

Mineralogy and chemical composition of ODP Sites 129-800 and 129-801

Sites 800 and 801 in the Pigafetta Basin allow the sedimentary history over the oldest remaining Pacific oceanic crust to be established. Six major deposition stages and events are defined by the main lithologic units from both sites. Mineralogical and chemical investigations were run on a large set of samples from these units. The data enable the evolution of the sediments and their depositional environments to be characterized in relation to the paleolatitudinal motion of the sites. The upper part of the basaltic crust at Site 801 displays a complex hydrothermal and alteration evolution expressed particularly by an ochre siliceous deposit comparable to that found in the Cyprus ophiolite. The oldest sedimentary cover at Site 801 was formed during the Callovian-Bathonian (stage 1) with red basal siliceous and metalliferous sediments similar to those found in supraophiolite sequences, and formed near an active ridge axis in an open ocean. Biosiliceous sedimentation prevailed throughout the Oxfordian to Campanian, with rare incursions of calcareous input during the middle Cretaceous (stages 2, 4, and 5). The biosiliceous sedimentation was drastically interrupted during the Aptian-Albian by thick volcaniclastic turbidite deposits (stage 3). The volcanogenic phases are pervasively altered and the successive secondary mineral parageneses (with smectites, celadonite, clinoptilolite, phillipsite, analcime, calcite, and quartz) define a "mineral stratigraphy" within these deposits. From this mineral stratigraphy, a similar lithologic layer is defined at the top of the Site 800 turbidite unit and the bottom of the Site 801 turbidite unit. Then, the two sites appear to have been located at the same distal distance from a volcanic source (hotspot). They crossed this locality, at about 10°S, at different times (latest Aptian for Site 800, middle Albian for Site 801). The Cretaceous siliceous sedimentation stopped during the late Campanian and was followed by deposition of Cenozoic pelagic red clay (stage 6). This deep-sea facies, which formed below the carbonate compensation depth, contains variable zeolite authigenesis in relation to the age of deposition, and records the global middle Cenozoic hiatus events. At the surface, the red clay from this part of the Pacific shows a greater detrital component than its equivalents from the central Pacific deep basins.