Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Minerals of bulk samples and clay fraction at DSDP Leg 80 Holes

At the request of the Leg 80 scientific party, selected samples of Cretaceous age were processed by X-ray diffraction at the mineralogy laboratories at the Ecole des Mines (Albian to Late Cretaceous samples) and at the Institut de Géologie at Dijon (Barremian samples). The results were used in developing the lithostratigraphy and sedimentology discussed in this volume by Rat et al. 1985 (doi:10.2973/dsdp.proc.80.140.1985) in their study of Barremian-Albian paleoenvironment, by Graciansky and Gillot in their study of Albian and Cenomanian limestones, and by Graciansky and Bourbon in their paleoenvironmental reconstructions for the Late Cretaceous chalks.

(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

Tratamento de lesões white spot pelo sistema fosfato de cálcio caseína-fosfopeptideo amorfo (CPP-ACP): prevenção secundária

Dissertação para obtenção do grau de Mestre no Instituto Superior de Ciências da Saúde Egas Moniz

(Table 1) Pore water halogen concentrations in ODP Holes 169-1033B and 169-1034B

The entire suite of halogens was measured in the pore fluids of Hole 1033B and 1034B from Saanich Inlet: ODP Leg 169S. The fast sedimentation rates and large amount of organic carbon burial coupled with anoxia of the overlying waters promotes an advanced stage of diagenesis within the sediment column. Chloride interstitial water profiles suggest salinity variations within the waters of Saanich Inlet. Concentration profiles for iodide and bromide support the argument that they are produced through the degradation of organic matter. Although the concentration increases in I- and Br- indicate that these halides are not regenerated in similar proportions to marine organic matter, it appears that iodide and bromide are regenerated to similar degrees within the sediment column and in similar proportions to the sediment halide concentrations. Fluoride porewater values show a complicated pattern, most likely caused by secondary reactions involving complexation with Mg2+, carbonate fluorapatite precipitation, carbonate mineral diagenesis, and/or uptake into alumino-silicate minerals.

Microstructure of Pharyngeal Tooth Enameloid in the Parrotfish Scarus rivulatus (Pisces:Scaridae)

The microstructure of parrotfish pharyngeal teeth was examined using scanning electron microscopy to infer possible mechanical properties of the dentition with respect to their function. Parrotfish tooth enameloid is formed from fluorapatite crystals grouped into bundles. In the upper and lower pharyngeal jaw, the majority of the crystal bundles are orientated either perpendicularly or vertically to the enameloid surface. The only exception is in the trailing apical enameloid in which the majority of bundles are orientated perpendicularly or horizontally to the trailing surface. A distinct transition occurs through the middle of the apex between the leading and trailing enameloid in teeth of the lower pharyngeal jaw. This transition appears less distinct in the teeth of the upper pharyngeal jaw. Enameloid microstructure indicates that shear forces predominate at the apex of the teeth. In the remainder of the enameloid, the microstructure indicates that wear is predominant, and the shear forces are of less importance.

Probing crystallisation of a fluoro-apatite - mullite system using neutron diffraction

Real-time small angle neutron scattering and wide angle neutron scattering studies were undertaken concurrently on a glass ionomer of nominal composition 4.5(SiO2)-3(Al2O3)-1.5(P2O5)-3(CaO)-2(CaF2). Neutron studies were conducted as a function of temperature to investigate the crystallisation process. No amorphous phase separation was observed at room temperature and the onset of crystallisation was found to occur at 650°C, which is 90°C lower than previously reported. The first crystalline phase observed corresponded to fluorapatite; it was only upon further heating was the mullite phase became present. The crystallite size at 650°C was found to be ~115Å and the result was consistent across all measurements.

Observations and rare earth element composition of manganese nodules during Atlantis cruise AT266, Blake Plateau

An area of about 22,000 km² on the northern Blake Plateau, off the coast of South Carolina, contains an estimated 2 billion metric tons of phosphorite concretions, and about 1.2 billion metric tons of mixed ferromanganese-phosphorite pavement. Other offshore phosphorites occur between the Blake Plateau and known continental deposits, buried under variable thicknesses of sediments. The phosphorite resembles other marine phosphorites in composition, consisting primarily of carbonate-fluorapatite, some calcite, minor quartz and other minerals. The apatite is optically pseudo-isotropic and contains about 6% [CO3]**2- replacing [PO4]**3- in its structure. JOIDES drillings and other evidence show that the phosphorite is a lag deposit derived from Miocene strata correlatable with phosphatic Middle Tertiary sediments on the continent. It has undergone variable cycles of erosion, reworking, partial dissolution and reprecipitation. Its present form varies from phosphatized carbonate debris, loose pellets, and pebbles, to continuous pavements, plates, and conglomeratic boulders weighing hundreds of kilograms. No primary phosphatization is currently taking place on the Blake Plateau. The primary phosphate-depositing environment involved reducing conditions and required at least temporary absence of the powerful Gulf Stream current that now sweeps the bottom of the Blake Plateau and has eroded away the bulk of the Hawthorne-equivalent sediments with which the phosphorites were once associated.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Chemistry of interstitial waters of ODP Leg 117 samples (Table 1)

Interstitial water analyses made at 12 sites during Leg 117 are used to define the nature of diagenetic reactions in organic-rich sediments on the Owen Ridge and Oman Margin. Minor variations in chloride concentration profiles are ascribed to past changes in bottom water salinity at two mid-depth margin sites and to upward migration of low salinity water at another. There is no evidence for subsurface brine movement, unlike the case on the Peru Margin. Dolomitization is widespread and accounts for the depletions of magnesium observed in pore waters at variable depths at nearly all sites. The mineral occurs both as disseminated euhedral limpid crystals and, in at least one location, in massive stringers. Formation of the latter is suggested to reflect precipitation during sea level transgressions when the sedimentation rate was low, but when productivity was high. Authigenic carbonate fluorapatite is also widespread, the phosphorus being derived from the breakdown of organic matter. Sulfate is quantitatively depleted at depth at most locations but the rate of depletion is markedly less than that observed on the Peru Margin where sedimentation is also similarly influenced by high rates of upwelling. The reason for this contrast is not clear and merits further investigation.

Extractions and analyses of reactive phosphorus in the Bering Sea from IODP Holes 323-U1341A and 323-U1341B

To reconstruct the cycling of reactive phosphorus (P) in the Bering Sea, a P speciation record covering the last ~ 4 Ma was generated from sediments recovered during Integrated Ocean Drilling Program (IODP) Expedition 323 at Site U1341 (Bowers Ridge). A chemical extraction procedure distinguishing between different operationally defined P fractions provides new insight into reactive P input, burial and diagenetic transformations. Reactive P mass accumulation rates (MARs) are ~ 20-110 µmol/cm2/ka, which is comparable to other open ocean locations but orders of magnitude lower than most upwelling settings. We find that authigenic carbonate fluorapatite (CFA) and opal-bound P are the dominant P fractions at Site U1341. An overall increasing contribution of CFA to total P with sediment depth is consistent with a gradual "sink switching" from more labile P fractions (fish remains, Fe oxides, organic matter) to stable authigenic CFA. However, the positive correlation of CFA with Al content implies that a significant portion of the supposedly reactive CFA is non-reactive "detrital contamination" by eolian and/or riverine CFA. In contrast to CFA, opal-bound P has rarely been studied in marine sediments. We find for the first time that opal-bound P directly correlates with excess silica contents. This P fraction was apparently available to biosiliceous phytoplankton at the time of sediment deposition and is a long-term sink for reactive P in the ocean, despite the likelihood for diagenetic re-mobilisation of this P at depth (indicated by increasing ratios of excess silica to opal-bound P). Average reactive P MARs at Site U1341 increase by ~ 25% if opal-bound P is accounted for, but decrease by ~ 25% if 50% of the extracted CFA fraction (based on the lowest CFA value at Site U1341) is assumed to be detrital. Combining our results with literature data, we present a qualitative perspective of terrestrial CFA and opal-bound P deposition in the modern ocean. Riverine CFA input has mostly been reported from continental shelves and margins draining P-rich lithologies, while eolian CFA input is found across wide ocean regions underlying the Northern Hemispheric "dust belt". Opal-bound P burial is important in the Southern Ocean, North Pacific, and likely in upwelling areas. Shifts in detrital CFA and opal-bound P deposition across ocean basins likely occurred over time, responding to changing weathering patterns, sea level, and biogenic opal deposition.

Pore water and solid phase geochemistry of sediment core US5B

Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (µXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40-50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (~4-8 wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.

(Table 1) Phosphorus and carbon chemistry of ODP Holes 169-1033B and 169-1034B

Uncertainty currently exists about the removal of carbon (C) and phosphorus (P) from the oceanic reservoir, especially in low oxygen settings. In this paper, the cycling of C and P is examined in sediments from the anoxic Saanich Inlet, cored by Ocean Drilling Program (ODP) Leg 169S in 1996 at two sites. Although Corg/Porg ratios are high and increase with depth in the Saanich Inlet, this effect is due largely to a remobilization of P from an organic matter sink to an authigenic sink. Reducible sedimentary components act as temporary shuttles in this process even in this anoxic setting, with the ultimate burial sink for the remobilized P being carbonate fluorapatite. The effective Corg/Preactive molar ratio appears to be about 150-200, indicating some preferential loss of P compared to C during organic matter degradation, but not approaching previously reported values of over 3000 in black shales. Reactive P accumulation rates in this basin range from 10,000-60,000 µmol/cm**2/kyr, greatly exceeding the range of 500-8000 µmol/cm**2/kyr found in most continental-margin settings, including regions of modern phosphogenesis. The initiation of marine sedimentation in the Saanich Inlet occurred after deglaciation, and the high rates of P burial seen here may provide an end-member example of the effects of sea level and margin sedimentation on the distribution of P within the marine P cycle.