Composition of palygorskite-rich and montmorillonite-rich zeolite-containing sediments from DSDP Sites 164 and 196

Cretaceous, Tertiary, and Quaternary sediments from Deep Sea Drilling Project Sites 164 and 196 (13°12' N, 161°31' W and 30°07' N, 148°34' E, respectively) were analyzed for major chemical elements and mineralogy. Sediments from these sites contain large proportions of authigenic minerals: mainly palygorskite, clinoptilolite and chert in the Cretaceous, and montmorillonite, phillipsite and chert in the Tertiary. The montmorillonite-phillipsite assemblage is thought to be derived from volcanic ash or glass, and the palygorskite-clinoptilolite assemblage is thought to be derived by reaction of biogenic silica with volcanic ash or glass or with montmorillonite and phillipsite. Both assemblages have generally moderate Ti/Al ratios, ranging from 0.026 to 0.047, so most of the palygorskite, clinoptilolite, montmorillonite and phillipsite could not be derived in situ from alteration of basaltic material. Plagioclase compositions suggest that the volcanic precursors were silicic or intermediate, but it is also possible that the sediments have been extensively fractionated by redistribution from nearby seamounts. Available data on other Late Cretaceous sediments in the Pacific were analyzed. Clinoptilolite and chert are present nearly everywhere where palygorskite is abundant; phillipsite is rare where palygorskite is abundant. It is suggested that increased water temperatures during the Cretaceous increased reaction rates and determined the alteration products.

Geochemistry and Hg isotopic composition of mid-Pleistocene sapropel of ODP Hole 161-974C

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average d202Hg value of -0.91 per mil ± 0.15 per mil (n = 5, 1 SD) and D199Hg value of 0.11 per mil ± 0.03 per mil (n = 5, 1 SD). Background sediments have an average d202Hg of -0.76 per mil ± 0.16 per mil (n = 5, 1 SD) and D199Hg of 0.05 per mil ± 0.01 per mil (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.

Geochemistry of sediment cores from the Rainbow vent site

A geochemical investigation was carried out on two sediment cores collected at 2 and 5 km from the Rainbow hydrothermal vent site. Bulk sediment compositions indicate that these cores record clear enrichments in Fe, Cu, Mn, V, P and As from hydrothermal plume fallout (Cave et al., 2002, doi:10.1016/S0016-7037(02)00823-2). Sequential dissolution of the bulk sediments has been used to discriminate between a leach (biogenic and oxy-hydroxide) component and a residual phase (detrital and sulphide/sulphate fractions). Major element data (Al, Fe, Ti, Mn, Mg, Ca, Si and index%) reveal that the hydrothermal input, as recorded in the leach phase, is much stronger than apparent from bulk sediment analyses alone. REE patterns for the leach phase record contributions from both biogenic carbonate (mimicking seawater REE patterns) and hydrothermal oxy-hydroxides, with the latter exhibiting positive Eu anomalies (hydrothermal derived) and negative Ce anomalies (seawater derived). Based on major element and REE data, the residue contains contributions from aeolian dust input, local MORB material and a hydrothermal component. Ternary REE mixing calculations indicate that most of the REE within the residual fraction (~80%) is derived from hydrothermal material, while detrital contributions to the REE budget, as deep-sea clay and volcanic debris, are <20%. By combining bulk and REE data for the various end-member components of the residue, we calculate that the chemical composition of the residue hydrothermal end-member is high in Ca (6-15%) and with a Nd/Sr ratio of 0.004. These characteristics indicate the presence of low-solubility hydrothermal sulphate (rather than sulphide) material within the residue component of Rainbow hydrothermal sediments.

Geochemical analysis of nine sections from the Nama Group, Namibia

The first appearance of skeletal metazoans in the late Ediacaran (~550 million years ago; Ma) has been linked to the widespread development of oxygenated oceanic conditions, but a precise spatial and temporal reconstruction of their evolution has not been resolved. Here we consider the evolution of ocean chemistry from ~550 to ~541 Ma across shelf-to-basin transects in the Zaris and Witputs Sub-Basins of the Nama Group, Namibia. New carbon isotope data capture the final stages of the Shuram/Wonoka deep negative C-isotope excursion, and these are complemented with a reconstruction of water column redox dynamics utilising Fe-S-C systematics and the distribution of skeletal and soft-bodied metazoans. Combined, these inter-basinal datasets provide insight into the potential role of ocean redox chemistry during this pivotal interval of major biological innovation. The strongly negative d13C values in the lower parts of the sections reflect both a secular, global change in the C-isotopic composition of Ediacaran seawater, as well as the influence of 'local' basinal effects as shown by the most negative d13C values occurring in the transition from distal to proximal ramp settings. Critical, though, is that the transition to positive d13C values postdates the appearance of calcified metazoans, indicating that the onset of biomineralization did not occur under post-excursion conditions. Significantly, we find that anoxic and ferruginous deeper water column conditions were prevalent during and after the transition to positive d13C that marks the end of the Shuram/Wonoka excursion. Thus, if the C isotope trend reflects the transition to global-scale oxygenation in the aftermath of the oxidation of a large-scale, isotopically light organic carbon pool, it was not sufficient to fully oxygenate the deep ocean. Both sub-basins reveal highly dynamic redox structures, where shallow, inner ramp settings experienced transient oxygenation. Anoxic conditions were caused either by episodic upwelling of deeper anoxic waters or higher rates of productivity. These settings supported short-lived and monospecific skeletal metazoan communities. By contrast, microbial (thrombolite) reefs, found in deeper inner- and mid-ramp settings, supported more biodiverse communities with complex ecologies and large skeletal metazoans. These long-lived reef communities, as well as Ediacaran soft-bodied biotas, are found particularly within transgressive systems, where oxygenation was persistent. We suggest that a mid-ramp position enabled physical ventilation mechanisms for shallow water column oxygenation to operate during flooding and transgressive sea-level rise. Our data support a prominent role for oxygen, and for stable oxygenated conditions in particular, in controlling both the distribution and ecology of Ediacaran skeletal metazoan communities.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Geochemistry of Neogene-Quaternary sediments in ODP Site 105-645

Subcontinuously cored early(?)-middle Miocene to recently deposited sediments from ODP Site 645 were studied texturally, mineralogically, and geochemically. The entire sequence contains minerals and associated chemical elements that are chiefly of detrital origin. In particular, the clay minerals, which include smectite, kaolinite, chlorite, and illite, are detrital. No obvious evidence of diagenesis with depth, of burial, of volcanism, or of hydrothermal alteration was observed. The sedimentary textures, clay mineralogy, and <2-µm fraction geochemistry of the early middle Miocene sediments (630 to 1147 mbsf) suggest the pronounced but variable influence of a southward bottom current. Two clay facies are defined. The lower one, Cj (780 to 1147 mbsf), is characterized by the great abundance of discrete smectite (with less than 15% illite interlayers), probably detrital in origin, and reworked older, discrete, smectite-rich sediments. The upper clay facies, C2 (630 to 780 mbsf), shows a net decrease of the fully expandable clay abundances, with a great abundance of mixed-layer, illite-smectite clays (60 to 80% of illite interlayers). Such clay assemblages can be inherited from paleosoils or older sedimentary rocks. An important change occurs at 630 mbsf (clay fraction) or 600 mbsf (sedimentary texture), which may be explained by the beginning of continental glaciation (630 mbsf, ~9 Ma) and the onset of ice rafting in Baffin Bay (600 mbsf, ~8 Ma). Above this level, the characteristics and modifications of the clay assemblages are controlled climatically and can be explained by the fluctuations of (1) ice-rafting, (2) speed of weak bottom currents, and (3) some supply by mud turbiditic currents. Three clay facies (C3, C4, and C5) can be defined by the abrupt increases of the inherited chlorite and illite clays.

Grain sizes and mineral composition of the basement of ODP Site 206-1256

Hole 1256C was cored 88.5 m into basement, and Hole 1256D, the deep reentry hole, was cored 502 m into basement during Ocean Drilling Program Leg 206. Hole 1256D is located ~30 m south of Hole 1256C (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). A thick massive flow drilled in both holes, Units 1256C-18 and 1256D-1, consists of a single cooling unit of cryptocrystalline to fine-grained basalt, interpreted as a ponded lava, 32 m and at least 74.2 m thick, respectively. This ponded flow gives us a unique opportunity to examine textural variations from the glassy, folded crust of the lava pond recovered from the top of Unit 1256C-18 through the coarse-grained, thick massive lava body to the unusually recrystallized and deformed base cored in Unit 1256C-18. Some detailed descriptions of the textures and grain size variations through the lava pond (Units 1256C-18 and 1256D-1), with special reference to the recrystallization of the base of Unit 1256C-18, are presented here.