999 resultados para geochimica


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Late Cretaceous (100-73 Ma) pelagic limestones were measured for helium concentration and isotopic composition to characterize the interplanetary dust flux using 3He as a tracer. In the Bottaccione section near Gubbio, Italy, three intervals of elevated 3He concentration were detected: K1 in the Campanian stage at ~79 Ma, K2 in the Santonian stage at ~ 85 Ma, and K3 in the Turonian stage at ~91 Ma. All three of these episodes are associated with high 3He/4He and 3He/non-carbonate ratios, consistent with their derivation from an enhanced extraterrestrial 3He flux rather than decreased carbonate sedimentation or dissolution. While K2 is modest in magnitude and duration and thus is of limited significance, K1 and K3 are each identified by a few myr interval with an ~4-fold enhancement in mean 3He flux compared with pre-event levels. Samples from ODP Hole 762C in the Indian Ocean spanning both K2 and K3 (93-83 Ma) confirm the presence of a peak in the Turonian stage, suggesting that K3 is a global event. The K1 and K3 3He events are similar in most respects to the two peaks previously detected in the Cenozoic, suggesting a similar origin. These have been attributed to a major asteroid collision in the Late Miocene and to a shower of either comets or asteroids in the Late Eocene. Based on the age and temporal evolution of K1, we suggest that it most likely records the collision which produced the Baptistina asteroid family independently dated at ~80 Ma. The K3 event is less easily explained. It is characterized by an unusually spiky and erratic temporal progression, suggesting an unusual abundance of very 3He rich particles not previously seen in the sedimentary 3He record. We suggest this episode arises either from a comet shower or from an asteroid shower possibly associated with dust-producing lunar impacts.

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The highly depleted intra-oceanic Tonga-Kermadec island arc forms an endmember of arc systems and a unique location in which to isolate the effects of the slab flux. High precision TIMS uranium, thorium, strontium, neodymium, and lead isotopes, along with complete major and trace element data, have been obtained on an extensive sample set comprising fifty-eight lavas along the arc as well as nineteen samples of the subducting sediments at DSDP site 204 just to the east of the Tonga-Kermadec trench. Ca/Ti and Al/Ti ratios extend from values appropriate to an N-MORB source in the southern Kermadecs to very high ratios in Tonga interpreted to reflect increasing degrees of depletion of the mantle wedge due to backarc basalt extraction. The isotope data emphasize the need for four components in the petrogenesis of the lavas: (1) the mantle wedge; (2) a component with elevated 207Pb/204Pb towards which the Kermadec and southern Tongan lavas extend; (3) a component characterised by high 206Pb/204Pb, Ta/Nd, and low 143Nd/144Nd observed only in the northernmost Tongan islands of Tafahi and Niuatoputapu; (4) a fluid component characterised by strong enrichments of Rb, Ba, U, K, Ph, and Sr, relative to Th, Zr, and the REE and producing large 238U excesses ((230Th/238U) = 0.8-0.5) in the more depleted lavas. The mantle wedge (Component 1) is isotopically similar to the source of the Lau BABB. Component 2 is average pelagic sediment on the downgoing Pacific plate as observed at DSDP sites 595/596 and in the upper sections of the sediment pile at DSDP site 204. Mass balance calculations indicate that less than 0.5% is recycled into the arc lavas; essentially all the subducted sediment is returned to the upper mantle (~0.03 km**3/yr). Exceptionally low concentrations of Ta and Nb relative to Th and the LREE requires that this sediment component is added as a partial melt which was in equilibrium with residual rutile or ilmenite. Component 3 is identified as volcaniclastics from the Louisville Ridge which comprise the lower 44 m of the sediment section intersected at DSDP site 204. These volcaniclastics are spatially restricted to the vicinity of the Louisville Ridge and provide a unique sediment tracer which can be used to show that it takes 4 Myr from the time of subduction to its first appearance in the arc lava signature. Component 4, the fluid contribution to the lava source is inferred to contribute ~1 ppm Rb, 10 ppm Ba, 0.02 ppm U, 600 ppm K, 0.2 ppm Ph, and 30 ppm Sr. It has 87Sr/86Sr = 0.7035 and 206Pb/204Pb = 18.5 and thus it is inferred to have been derived from dehydration of the subducting altered oceanic crust. U-Th isotope disequilibria reflect the time since fluid release from the subducting slab and a reference line through the lowest (230Th/232Th) lavas constrains this to be 30000-50000 yr. The U-Th and Th-Ra isotope systematics are decoupled, and it is suggested that Th-Ra isotope disequilibria record the time since partial melting and thus indicate rapid channelled magma ascent. Olivine gabbro xenoliths from Raoul are interpreted as cumulates to their host lavas with which they form zero age U-Th isochrons indicating that minimal time was spent in magma chambers. The subduction signature is not observed in lavas from the backarc island of Niuafo'ou. These were derived from partial melting of fertile peridotite at 130-160 km depth with melt rates around 0.0002 kg/m**3/yr.

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Above the Walvis Ridge, in the SE Atlantic Ocean, we collected living plantkic foraminifera from the upper water column using depth stratified plantkon tows. The oxygen isotope composition (d18Oc) in shells of foraminifera and shell concentration profiles show seasonal and depth habitats of individual species. The tow results are compared with the average annual deposition d18Oc from sediment traps and the interannual average d18Oc of fossil specimens in top sediments at the same site. The species Globigerinita glutinata best reflects the austral winter/spring sea surface temperature (SST). Its d18Oc signal in top sediments remains pristine. In contrast, tow results also show that Globigerinoides ruber continues to calcify below the surface mixed layer (SML), i.e., down to the deep chlorophyll maximum (DCM); hence its d18Oc signature of exported specimens reflects the SST only when SML incorporates the DCM. Deep tow and sediment trap results show that both Globorotalia truncatulinoides and Globorotalia inflata record the temperature between 150 and 350 m, depending on the season and the shell size. However, for all fossil taxa in sediments apart from Globigerinita glutinata, we observe a positive d18Oc shift with respect to the sediment trap and plankton tow values, likely related to the interannual flux changes and deep encrustation.

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We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

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Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb (206Pb/204Pb up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and 143Nd/144Nd increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas. Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of "normal" depleted MORB.

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Porewater concentrations of sulfate, methane, and other relevant constituents were determined on four sediment cores from the high productivity upwelling area off Namibia which were recovered from the continental slope at water depths of 1300 and 2000 m. At all four stations a distinct sulfate-methane transition zone was observed several meters below the seafloor in which both sulfate and methane are consumed. Nutrient porewater concentration profiles do not show gradient slope changes at the depths of the transition zones. Flux calculations carried out on the basis of the determined porewater profiles revealed that anaerobic methane oxidation accounts for 100% of deep sulfate reduction within the sulfate-methane transition zone and consumes the total net diffusive sulfate flux. A significant contribution of organic carbon oxidation to the reduction of sulfate at these depths could, therefore, be excluded. We state that porewater profiles of sulfate with constant gradients above the transition zones are indicative for anaerobic methane oxidation controlling sulfate reduction.

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From the experimental data on stepwise thermal release of neutron induced 39Ar (39K (n, p) 39Ar) from rocks and minerals, Arrhenius plots were constructed, which gave activation energies for the thermal release process. The activation energies for DSDP Leg 58 and Leg 60 submarine volcanic rocks range from 12 to 20 kcal/mol, whereas those for granodiorites and the K-feldspar separates have activation energies ranging from 37 to 48 kcal/mol. The smaller activation energies for the submarine volcanic rocks reflect the grain boundary diffusion process, while the thermal diffusion of 39Ar from granodiorites and K-feldspar is essentially controlled by a volume diffusion. The grain boundary diffusion for the submarine volcanic rocks suggests that K resides essentially in the grain boundaries.

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Siwalik paleosol and Bengal Fan sediment samples were analyzed for the abundance and isotopic composition of n-alkanes in order to test for molecular evidence of the expansion of C4 grasslands on the Indian subcontinent. The carbon isotopic compositions of high-molecular-weight alkanes in both the ancient soils and sediments record a shift from low d13C values (ca. -30 per mil) to higher values (ca. -22 per mil) prior to 6 Ma. This shift is similar in magnitude to that recorded by paleosol carbonate and fossil teeth, and is consistent with a relatively rapid transition from dominantly C3 vegetation to an ecosystem dominated by C4 plants typical of semi-arid grasslands. The n-alkane values from our paleosol samples indicate that the isotopic change began as early as 9 Ma, reflecting either a growing contribution of C4 plants to a dominantly C3 biomass or a decrease in water availability to C3 plants. Molecular and isotopic analyses of other compounds, including n-alcohols and low-molecular weight n-alkanes indicate paleosol organic matter contains contributions from a mixture of sources, including vascular plants, algae and/or cyanobacteria and microorganisms. A range of inputs is likewise reflected in the isotopic composition of the total organic carbon from these samples. In addition, the n-alkanes from two samples show little evidence for pedegenic inputs and we suggest the compounds were derived instead from the paleosol's parent materials. We suggest the record of vegetation in ancient terrestrial ecosystems is better reconstructed using isotopic signatures of molecular markers, rather than bulk organic carbon. This approach provides a means of expanding the spatial and temporal records of C4 plant biomass which will help to resolve possible tectonic, climatic or biological controls on the rise of this important component of the terrestrial biosphere.

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Microthermometric and isotopic analyses of fluid inclusions in primitive olivine gabbros, oxide gabbros, and evolved granitic material recovered from Ocean Drilling Program Hole 735B at the Southwest Indian Ridge provide new insights into the evolution of C-O-H-NaCl fluids in the plutonic foundation of the oceanic crust. The variably altered and deformed plutonic rocks span a crustal section of over 1500 m and record a remarkably complex magma-hydrothermal history. Magmatic fluids within this suite followed two chemically distinct paths during cooling through the subsolidus regime: the first path included formation of CO2+CH4+H2O+C fluids with up to 43 mole% CH4; the second path produced hypersaline brines that contain up to 50% NaCl equivalent salinities. Subsequent to devolatilization, respeciation of magmatic CO2, attendant graphite precipitation, and cooling from 800°C to 500°C promoted formation of CH4-enriched fluids. These fluids are characterized by average d13C(CH4) values of -27.1+/-4.3 per mil (N=45) with associated d13C(CO2) compositions ranging from -24.9 per mil to -1.9 per mil (N=39), and average dD values of exsolved vapor of -41+/-12 per mil (N=23). In pods, veins, and lenses of highly fractionated residual material, hypersaline brines formed during condensation and by direct exsolution in the absence of a conjugate vapor phase. Entrapped CO2+CH4+H2O-rich fluids within many oxide-bearing rocks and felsic zones are significantly depleted in 13C (with d13C(CO2) values down to about -25 per mil) and contain CO2 concentrations higher than those predicted by equilibrium devolatilization models. We hypothesize that lower effective pressures in high-temperature shear zones promoted infiltration of highly fractionated melts and compositionally evolved volatiles into focused zones of deformation, significantly weakening the rock strength. In felsic-rich zones, volatile build-up may have driven hydraulic fracturing of gabbroic wall rocks resulting in the formation of magmatic breccias. Comparison of isotopic compositions of fluids in plutonic rocks from 735B, the MARK area of the Mid-Atlantic Ridge, and the Mid-Cayman Rise indicate (1) that the carbon isotope composition of the lower oceanic crust may be far more heterogeneous than previously believed and (2) that carbon-bearing species in the oceanic crust and their distribution at depth are highly variable.

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Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.

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Sr isotope analyses have been conducted on anhydrite samples from the TAG (Trans-Atlantic Geotraverse) active hydrothermal mound (26°08?N, Mid-Atlantic Ridge) that have previously been shown to exhibit two distinct patterns of REE behavior when normalized to TAG end-member hydrothermal fluid. Despite differences in REE patterns, the Sr isotope data indicate that all the anhydrites precipitated from fluids with a similar range of hydrothermal fluid and seawater components, and all but one were seawater-dominated (52%-75%). Speciation calculations using the EQ3/6 software package for geochemical modeling of aqueous systems suggest that the REE complexation behavior in different fluid mixing scenarios can explain the variations in the REE patterns. Anhydrites that exhibit relatively flat REE patterns [(La_bs)/(Yb_bs) = 0.8-2.0; subscript bs indicates normalization to end-member black smoker hydrothermal fluid] and a small or no Eu anomaly [(Eu_bs)/(Eu*_bs) = 0.8-2.0] are inferred to have precipitated from mixes of end-member hydrothermal fluid and cold seawater. REE complexes with hard ligands (e.g., fluoride and chloride) are less stable at low temperatures and trivalent Eu has an ionic radius similar to that of Ca2+ and the other REE, and so they behave coherently. In contrast, anhydrites that exhibit slight LREE-depletion [(La_bs)/(Yb_bs) = 0.4-1.4] and a distinct negative anomaly [(Eu_bs)/(Eu*_bs) = 0.2-0.8] are inferred to have precipitated from mixes of end-member hydrothermal fluid and conductively heated seawater. The LREE depletion results from the presence of very stable LREE chloro-complexes that effectively limit the availability of the LREE for partitioning into anhydrite. Above 250°C, Eu is present only in divalent form as chloride complexes, and discrimination against Eu2+ is likely due to both the mismatch in ionic radii between Eu2+ and Ca2+, and the strong chloro-complexation of divalent Eu which promotes stability in the fluid and inhibits partitioning of Eu2+ into precipitating anhydrite. These variations in REE behavior attest to rapid fluctuations in thermal regime, fluid flow and mixing in the subsurface of the TAG mound that give rise to heterogeneity in the formation conditions of individual anhydrite crystals.

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The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

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Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

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Seven manganese nodules, eight ferromanganiferous shales from the Cretaceous Wai Bua Formation of Timor, and a pelagic limestone with four ferromanganese enriched layers from the Middle Eocene of Timor have been analysed. The nodules are compared with modern deep-sea nodules, and the ferromanganiferous shales are contrasted with relatively shallow marine manganiferous shales. The conclusion is reached that these rocks from Timor were probably deposited in a bathypelagic environment. There is a total absence of any indication that volcanic material has contributed to these deposits. The chemical composition of the ferromanganiferous rocks are discussed and some indications of biogenic influences are noted. The Middle Eocene pelagic limestone is compared with a similar modern sediment described from the Easter Island Rise in the Pacific.

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The solution rate of biogenic opal in near-surface sediments in the Central Equatorial Pacific is three to eight orders of magnitude lower than similar acid-cleaned samples. Iron, magnesium and calcium aluminosilicates may be the minerals which are forming on the surface of the opal and reducing its solution rate. The scale height of the system studied suggests that diffusive and not advective processes are primarily responsible for the removal of dissolved silica in sediments. Solution budget calculations for this area suggest that 90-99 per cent of the biogenic opal produced in surface waters dissolves before reaching the sediment-water interface; an additional amount dissolves within the sediment and diffuses into bottom waters leaving 0.05-0.15 per cent of the original amount of opal produced by organisms in the sedimentary record. The relative solution potential of the upper 1000 m of the water column varies by more than an order of magnitude from the Antarctic to Equator and may have a pronounced effect on the accumulation rate of biogenic opal in underlying sediments.