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.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Calcium carbonate, organic carbon, d13C and C/N composition of ODP Sites 186-1150 and 186-1151

Past changes in sea-surface productivity in the Oyashio Current are evaluated on the basis of abundances of biological constituents in sediments from Leg 186 sites. Organic carbon contents at Sites 1150 and 1151 are moderate (0.5 to 1.5 wt%) and have an algal origin as indicated by low C/N ratios (<10) and by carbon isotopic compositions ranging from -23.4 to -21.3. A decreasing trend in organic carbon contents, carbon isotope ratios, and C/N ratios occurs with depth at both sites, probably as a consequence of diagenetic degradation of organic matter. Mass accumulation rates (MARs) determined for organic carbon and carbonates at Sites 1150 and 1151 show an abrupt increase between ~5 and 7 Ma. Similar results have been reported for sites in the Indian Ocean and the Pacific Ocean for the same time interval. As it has been previously suggested, the observed increase in MAR for both carbonate and organic carbon at Leg 186 sites probably resulted from augmented nutrient supply either from continental sources or from a more vigorous ocean circulation.

Subdivisions of the sediment column, carbon and calcium carbonate at DSDP Hole 64-480

We analyzed 580 integrated scrape-samples from HPC Site 480 for organic and carbonate carbon. Once precise dating is available, these will provide a high-resolution framework for understanding late Quaternary Oceanographic and climatic fluctuations in this region. Organic carbon ranges mostly within a narrow band of 1.8 to 3.5% C. Calcium carbonate varies from undetectable to over 20%, with an average of only about 5%. Source of carbonate are mostly benthic and planktonic foraminifers, although some sections are dominated by diagenetic carbonate, shelly hash, or nannofossils. Detrital sources are low in carbonate. We divided the sequence into 17 calcium carbonate (CC) zones to separate pulses, low and median values. The CC-Zones show various second-order patterns of cyclicity, asymmetry, and events. Laminated zones have lowest uniform values, but a perfect correlation between carbonate content and homogeneous or laminated facies was not found. Maximum values tend to be located near the transition of these two sediment types, showing that accumulation of carbonate is favored during times of breakdown of stable Oceanographic conditions.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Chemistry of zeolithe and clays from Central Kerguelen Plateau basalts

Ocean Drilling Program Leg 120 recovered basement samples that consisted of zeolite-facies metabasalts at Sites 747, 749, and 750 on the Kerguelen Plateau. These basalts were metamorphosed in the low to intermediate zones of the zeolite facies, as indicated by the presence of diagnostic zeolites and the absence of chlorite, epidote, prehnite, pumpellyite, and wairakite. Chabazite, natrolite, thompsonite, mesolite, stilbite, huelandite, and smectites occur as amygduloidal fillings in basalts from Holes 747C and 750B, whereas only stilbite, laumontite, and pure and mixed-layered smectites were identified in amygduloidal basalts from Hole 749C. In the lower sections of Hole 749C, only laumontite and mixed-layered smectites coexist. Based on calculations with published experimental phase equilibria, the absence of wairakite in basalts from Hole 749C and of laumontite in basalts from Holes 747C and 750B suggests that metamorphic temperatures did not exceed approximately 225° and 120°C, respectively. The presence of well-developed zeolite mineral assemblages and the absence of carbonate and clay mineral assemblages restricts XCO2 in the fluid to approximately <=0.0075. Low- to intermediate-zone zeolite-facies mineral assemblages in basalts from the Kerguelen Plateau can be accounted for by metamorphism in an active geothermal area such as present-day Iceland.

Foraminiferal assemblages and stable isotopes across the early Paleogene carbonate facies of Perth Abyssal Plain off Western Australia

Bulk carbonate content, planktic and benthic foraminiferal assemblages, stable isotope compositions of bulk carbonate and Nuttallides truempyi (benthic foraminifera), and non-carbonate mineralogy were examined across ~30 m of carbonate-rich Paleogene sediment at Deep Sea Drilling Project (DSDP) Site 259, on Perth Abyssal Plain off Western Australia. Carbonate content, mostly reflecting nannofossil abundance, ranges from 3 to 80% and generally exceeds 50% between 35 and 57 mbsf. A clay-rich horizon with a carbonate content of about 37% occurs between 55.17 and 55.37 mbsf. The carbonate-rich interval spans planktic foraminiferal zones P4c to P6b (~57-52 Ma), with the clay-rich horizon near the base of our Zone P5 (upper)-P6b. Throughout the studied interval, benthic species dominate foraminiferal assemblages, with scarce planktic foraminifera usually of poor preservation and limited species diversity. A prominent Benthic Foraminiferal Extinction Event (BFEE) occurs across the clay-rich horizon, with an influx of large Acarinina immediately above. The delta13C records of bulk carbonate and N. truempyi exhibit trends similar to those observed in upper Paleocene-lower Eocene (~57-52 Ma) sediment from other locations. Two successive decreases in bulk carbonate and N. truempyi delta13C of 0.5 and 1.0? characterize the interval at and immediately above the BFEE. Despite major changes in carbonate content, foraminiferal assemblages and carbon isotopes, the mineralogy of the non-carbonate fraction consistently comprises expanding clay, heulandite (zeolite), quartz, feldspar (sodic or calcic), minor mica, and pyrolusite (MnO2). The uniformity of this mineral assemblage suggests that Site 259 received similar non-carbonate sediment before, during and after pelagic carbonate deposition. The carbonate plug at Site 259 probably represents a drop in the CCD from ~57 to 52-51 Ma, as also recognized at other locations.

Composition and distribution of silica in sediments of the Broken Ridge

Within a dipping sequence of middle Cretaceous to Eocene sediments on Broken Ridge, opal-A, opal-CT, and quartz occur as minor constituents in carbonate and ash-rich sediments. Biogenic opal-A is mainly derived from diatoms and radiolarians. Opal-A and almost all siliceous microfossils disappear within a narrow (<20-m-thick) transition zone below which authigenic opal-CT and quartz are present. These latter silica polymorphs occur together within a 750-m-thick interval, but the ratio of quartz/opal-CT increases with increasing age and depth within the pre-rift sediment sequence. The boundary between opal-A- and opal-CT-bearing sediments is also a physical boundary at which density, P-wave velocity, and acoustic impedance change. This physical transition is probably caused by infilling of pore space by opal-CT lepispheres.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Sedimentary facies, clay mineralogy and geochemistry of the Paleogene sediments of ODP Site 105-647

Claystones immediately overlying the early Eocene age ocean-floor basalt, cored at Ocean Drilling Program (ODP) Site 647, underwent hydrothermal and thermal alterations originating from the basalt, which resulted in changes in both the mineralogical and chemical composition of the sediments. Chlorites and higher magnesium and iron concentrations were found in the lowermost sediment sequence. Upcore, changes in the bulk chemical composition of the sediments become smaller, when compensated for variations in the carbonate content originating from biogenic and authigenic components. Chlorite disappears upcore, but still only part of the swelling clay minerals have survived the thermal influence. Thirty meters above the basalt, the clay mineralogy and chemical composition become uniform throughout the Paleogene section. Iron-rich smectites (i.e., nontronitic types), totally dominate the clay mineral assemblage. Biogenic components, responsible for the dominant part of the calcite and cristobalite contents, vary in amount in the upper part, and so do the authigenic carbonate and sulfide contents. Detrital components, such as kaolinite, illite, quartz, and feldspars, make up a very small proportion of the sediment record. The nontronitic smectites are believed to be authigenic, formed by a supply of iron from the continuous formation of ocean-floor basalt in the ridge area that reacted with the detrital and biogenic silicates and alumina silicates.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

Geochemistry and mineralogy of ultramafic rocks from conical seamount

The Mariana arc-trench system, the easternmost of a series of backarc basins and intervening remnant arcs that form the eastern edge of the Philippine Sea Plate, is a well-known example of an intraoceanic convergence zone. Its evolution has been studied by numerous investigators over nearly two decades (e.g., Kang, 1971; Uyeda and Kanamori, 1979; LaTraille and Hussong, 1980; Fryer and Hussong, 1981; Mrosowski et al., 1982; Hussong and Uyeda, 1981; Bloomer and Hawkins, 1983; Karig and Ranken, 1983; McCabe and Uyeda, 1983; Hsui and Youngquist, 1985; Fryer and Fryer, 1987; Johnson and Fryer, 1988; Johnson and Fryer, 1989; Johnson et al., 1991). The Mariana forearc has undergone extensive vertical uplift and subsidence in response to seamount collision, to tensional and rotational fracturing associated with adjustments to plate subduction, and to changes in the configuration of the arc (Hussong and Uyeda, 1981; Fryer et al., 1985). Serpentine seamounts, up to 2500 m high and 30 km in diameter, occur in a broad zone along the outer-arc high (Fryer et al., 1985; Fryer and Fryer, 1987). These seamounts may be horsts of serpentinized ultramafic rocks or may have been formed by the extrusion of serpentine muds. Conical Seamount, one of these serpentine seamounts, is located within this broad zone of forearc seamounts, about 80 km from the trench axis, at about 19°30'N. The seamount is approximately 20 km in diameter and rises 1500 m above the surrounding seafloor. Alvin submersible, R/V Sonne bottom photography, seismic reflection, and SeaMARC II studies indicate that the surface of this seamount is composed of unconsolidated serpentine muds that contain clasts of serpentinized ultramafic and metamorphosed mafic rocks, and authigenic carbonate and silicate minerals (Saboda et al., 1987; Haggerty, 1987; Fryer et al., 1990; Saboda, 1991). During Leg 125, three sites were drilled (two flank sites and one summit site) on Conical Seamount to investigate the origin and evolution of the seamount. Site 778 (19°29.93'N, 146°39.94'E) is located in the midflank region of the southern quadrant of Conical Seamount at a depth of 3913.7 meters below sea level (mbsl) (Fig. 2). This site is located in the center of a major region of serpentine flows (Fryer et al., 1985, 1990). Site 779 (19°30.75'N, 146°41.75'E), about 3.5 km northeast of Site 778, is located approximately in the midflank region of the southeast quadrant of Conical Seamount, at a depth of 3947.2 mbsl. This area is mantled by a pelagic sediment cover, overlying exposures of unconsolidated serpentine muds that contain serpentinized clasts of mafic and ultramafic rocks (Fryer et al., 1985, 1990). Site 780 (19°32.5'N, 146°39.2'E) is located on the western side of Conical Seamount near the summit, at a depth of 3083.4 mbsl. This area is only partly sediment covered and lies near active venting fields where chimney structures are forming (Fryer et al., 1990).

Age and oxygen isotope data for bulk carbonate from DSDP Sites 41-366 and 72-516 and ODP Sites 111-677A and 130-807

A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured d18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal d18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and d18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal d18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured d18O values of Eocene bulk carbonates are more than 2? lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate d180 values particularly sensitive to diagenetic effects; most of the observed variations in measured d18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.

Seawater carbonate chemistry and calcium carbonate of Padina spp., photosynthesis of Padina pavonica in nature CO2 gradients experiment

Predicting the impacts of ocean acidification on coastal ecosystems requires an understanding of the effects on macroalgae and their grazers, as these underpin the ecology of rocky shores. Whilst calcified coralline algae (Rhodophyta) appear to be especially vulnerable to ocean acidification, there is a lack of information concerning calcified brown algae (Phaeophyta), which are not obligate calcifiers but are still important producers of calcium carbonate and organic matter in shallow coastal waters. Here, we compare ecological shifts in subtidal rocky shore systems along CO2 gradients created by volcanic seeps in the Mediterranean and Papua New Guinea, focussing on abundant macroalgae and grazing sea urchins. In both the temperate and tropical systems the abundances of grazing sea urchins declined dramatically along CO2 gradients. Temperate and tropical species of the calcifying macroalgal genus Padina (Dictyoaceae, Phaeophyta) showed reductions in CaCO3 content with CO2 enrichment. In contrast to other studies of calcified macroalgae, however, we observed an increase in the abundance of Padina spp. in acidified conditions. Reduced sea urchin grazing pressure and significant increases in photosynthetic rates may explain the unexpected success of decalcified Padina spp. at elevated levels of CO2. This is the first study to provide a comparison of ecological changes along CO2 gradients between temperate and tropical rocky shores. The similarities we found in the responses of Padina spp. and sea urchin abundance at several vent systems increases confidence in predictions of the ecological impacts of ocean acidification over a large geographical range.