Joris M. Gieskes

Diagenesis of siliceous oozes—I. Chemical controls on the rate of opal-A to opal-CT transformation—an experimental study

Abstract Evidence from deep-sea sediments supports the following diagenetic maturation sequence: opal-A (siliceous ooze) → opal-CT (porcelanite) → chalcedony or cryptocrystalline quartz (chert). A solution-redeposition mechanism is involved in the opal-A to opal-CT transformation. Exceptions to the overall maturation sequence are numerous, suggesting that temperature and time are not the only important factors controlling these mineralogical transformations. The rates of the above transformations are strongly affected by the composition of the solution and of the host sediments ; in Mesozoic clayey sediments, opal-CT predominates, while in carbonate sediments quartz is most common. Experiments at 25 and 150°C over a period of one day to six months show that the transformation rate of opal-A to opal-CT is much higher in carbonate than in clay-rich sediments, and that opal-CT lepisphere formation is aided by the precipitation of nuclei with magnesium hydroxide as an important component. The role of carbonate is explained as follows : in carbonate-rich sediments, the dissolution of carbonate provides the necessary alkalinity, and sea water provides the magnesium for the magnesium hydroxide in the nuclei. In contrast, in clay-rich sediments the clay minerals compete with opal-CT formation for the available alkalinity from sea water. As a result, the clays are enriched in Mg, and the rate of opal-CT formation is strongly reduced. This mechanism also bears on the common observation of carbonate replacement by silica.

Trace element behavior in hydrothermal experiments: Implications for fluid processes at shallow depths in subduction zones

Chemical evaluation of fluids affected during progressive water-sediment interactions provides critical information regarding the role of slab dehydration and/or crustal recycling in subduction zones. To place some constraints on geochemical processes during sediment subduction, reactions between decollement sediments and synthetic NaCl-CaCl2 solutions at 25–350°C and 800 bar were monitored in laboratory hydrothermal experiments using an autoclave apparatus. This is the first attempt in a single set of experiments to investigate the relative mobilities of many subduction zone volatiles and trace elements but, because of difficulties in conducting hydrothermal experiments on sediments at high P-T conditions, the experiments could only be designed for a shallow (∼ 10 km) depth. The experimental results demonstrate mobilization of volatiles (B and NH4) and incompatible elements (As, Be, Cs, Li, Pb, Rb) in hydrothermal fluids at relatively low temperatures (∼ 300°C). In addition, a limited fractionation of light from heavy rare earth elements (REEs) occurs under hydrothermal conditions. On the other hand, the high field strength elements (HFSEs) Cr, Hf, Nb, Ta, Ti, and Zr are not mobile in the reacted fluids. The observed behavior of volatiles and trace elements in hydrothermal fluids is similar to the observed enrichment in As, B, Cs, Li, Pb, Rb, and light REEs and depletion in HFSEs in arc magmas relative to magmas derived directly from the upper mantle. Thus, our work suggests a link between relative mobilities of trace elements in hydrothermal fluids and deep arc magma generation in subduction zones. The experimental results are highly consistent with the proposal that the addition of subduction zone hydrous fluids to the subarc mantle, which has been depleted by previous melting events, can produce the unique characteristics of arc magmas. Moreover, the results suggest that deeply subducted sediments may no longer have the composition necessary to generate the other distinct characteristics, such as the B-δ11 B and B-10Be systematics, of arc lavas. Finally, the mobilization of B, Cs, Pb, and light REEs relative to heavy REEs in the hydrothermal fluids fractionate the ratios of B/Be, B/Nb, Cs/Rb, Pb/Ce, La/Ba and LREE/HREE, which behave conservatively during normal magmatic processes. These results demonstrate that the composition of slab-derived fluids has great implications for the recycling of elements; not only in arc magmas but also in mantle plumes.

Interstitial water trace-metal chemistry of laminated sediments from the Gulf of California, Mexico

Abstract This report presents major and minor element profiles for interstitial waters recovered from the oxygen-minimum zone of the Gulf of California. The major elements and nutrients show concentration-depth profiles typical for anoxic, laminated sediments, with sulfate-reduction occurring close to the sediment-water interface, accompanied by increases in alkalinity and ammonia. Barium is solubilized near the sediment-water interface, but decreases below 10 cm depth, showing concentrations consistent with barite solubility. The dissolved concentrations of Mn, Fe, and Al are higher in the upper part of the sedimentary column; Mn and Fe due to reduction of oxides and Al probably because of dissolution of siliceous material. In contrast, dissolved Mo, V, and Cr show concentrations increasing with depth. The strong correlation of the concentrations of Mo, V and Cr with “yellow substance” absorbance reflect the importance of dissolved organic matter for the mobility of these elements during early diagenesis.

Tectonics and hydrogeology of the northern Barbados Ridge: Results from Ocean Drilling Program Leg 110

Drilling near the deformation front of the northern Barbados Ridge cored an accretionary prism consisting of imbricately thrusted Neogene hemipelagic sediments detached from little-deformed Oligocene to Campanian underthrust deposits by a decollement zone composed of lower Miocene to upper Oligocene, scaly radiolarian claystone. Biostrati-graphically defined age inversions define thrust faults in the accretionary prism that correlate between sites and are apparent on the seismic reflection sections. Two sites located 12 and 17 km west of the deformation front document continuing deformation of the accreted sediments during their uplift. Deformational features include both large- and small-scale folding and continued thrust faulting with the development of stratal disruption, cataclastic shear zones, and the proliferation of scaly fabrics. These features, resembling structures of accretionary complexes exposed on land, have developed in sediments never buried more than 400 m and retaining 40% to 50% porosity. A single oceanic reference site, located 6 km east of the deformation front, shows incipient deformation at the stratigraphic level of the decollement and pore-water chemistry anomalies both at the decollement level and in a subjacent permeable sand interval. Pore-water chemistry data from all sites define two fluid realms: one characterized by methane and chloride anomalies and located within and below the decollement zone and a second marked solely by chloride anomalies and occurring within the accretionary prism. The thermogenic methane in the decollement zone requires fluid transport many tens of kilometers arcward of the deformation front along the shallowly inclined decollement surface, with minimal leakage into the overlying accretionary prism. Chloride anomalies along faults and a permeable sand layer in the underthrust sequence may be caused by membrane filtration or smectite dewatering at depth. Low matrix permeability requires that fluid flow along faults occurs through fracture permeability. Temperature and geochemical data suggest that episodic fluid flow occurs along faults, probably as a result of deformational pumping.

LITHIUM ISOTOPE GEOCHEMISTRY OF SEDIMENTS AND HYDROTHERMAL FLUIDS OF THE GUAYMAS BASIN, GULF OF CALIFORNIA

Abstract Lithium isotopic compositions of hydrothermally altered sediments of Deep Sea Drilling Project (DSDP) site 477/477A, as well as high temperature vent fluids of the Guaymas Basin, have been determined to gain an understanding of lithium exchange during fluid-sediment interaction at this sediment-covered spreading center. Unaltered turbidite of the basin has a δ 6 Li value of −10%., 5–7%. heavier than fresh oceanic basalts. Contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value (−8%.). Below the sill, sediments altered by a deep-seated hydrothermal system show strong depletions in lithium, while lithium isotopic compositions vary greatly, ranging from −11 to +1 %.. The shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals. The complexity of the isotope profile is attributed to inhomogeneity in mineral composition, the tortuous pathway of fluids and the temperature effect on isotopic fractionation. The range of lithium concentration and δ 6 Li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment-free mid-ocean ridge systems. The lack of a distinct expression of sediment input is explained in terms of a flow-through system with continuous water recharge. The observations on the natural system agree well with the results of laboratory hydrothermal experiments. The experimental study demonstrates the importance of temperature, pressure, water/rock ratio, substrate composition and reaction time on the lithium isotopic composition of the reacted fluid. High temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as Guaymas are a source of lithium to the ocean. The ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones.

Sediment deformation and hydrogeology of the Nankai Trough accretionary prism: Synthesis of shipboard results of ODP Leg 131

The main objective of Leg 131 was to provide data on the deformational processes and associated hydrogeology of the Nankai prism toe. Drilling succeeded, for the first time in the history of ocean drilling, in penetrating the complete sedimentary sequence to basaltic basement, reaching 1327 mbsf (metres below seafloor) with good core recovery (55%). Excellent correlation of the lithology and structure, including the frontal thrust and the decollement, with seismic reflection images was also determined. Bedding dips, faults and shear bands analyzed in the cores confirm the pattern of deformation to be mainly due to NW-SE shortening, as expected from the plate tectonic convergence vector. Below the decollement, no significant deformation features were observed, indicating that the decollement is a sharp discontinuity in stress transmission. Physical properties data show major discontinuities at the decollement, notably an increase in porosity below the later. This may indicate excess pore pressure in the subducted section and decollement zone. A less marked increase in porosity below the frontal thrust may reflect the youthfulness of this feature. Attempts to make downhole measurements were severely hampered by unstable hole conditions, but useful constraints have been placed on the thermal regime, and some calibration of laboratory physical properties toin-situ conditions has been provided, andin-situ stress and pore pressure were measured in the uppermost sediments. Evidence of channelized fluid flows is inconclusive. No sharp geochemical signatures or unequivocal geochemical anomalies indicative of channelized fluid flow were found. Thermal measurements are not significantly different from those predicted by a purely conductive heat flow model. A signature of low chloride pore water near the decollement may partly be related to smectite diagenesis but may also be due to episodic fluid flow events. We conclude that dewatering probably occurred dominantly through diffuse flow throughout the accreted sediments at this site.

On the calculation of the degree of saturation of sea water with respect to calcium carbonate under in situ conditions

Abstract A discussion is presented of the computation of the in situ degree of saturation of sea water with respect to calcite or aragonite, Ω, using apparent thermodynamic constants. It is found that when the various reported values of the constants are recomputed so as to be strictly comparable the resulting concordance is generally good. A systematic error in Ω of not more than 10 per cent is estimated to result from the uncertainties in the constants. This is equivalent to an error of 1 per cent in the measured values of A t or ΣCO 2 . A profile of A t and ΣCO 2 from the Brazil Basin in the equatorial South Atlantic is used as an example of the computation procedure.

Bromine and iodine in Peru margin sediments and pore fluids: Implications for fluid origins

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl≈ concentrations. The slope pore fluids are characterized by low Cl− concentrations, but elevated Br− and I− concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl− and Br− concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br−, I−, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I− concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br− concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I− and the I− enrichments relative to NH4+ and Br− correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I−Br− ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl− concentrations. Other possible sources for low Cl− water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl− fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment IBr ratios. Comparison of Na+Cl− and Br−Cl− molar ratios in the pore fluids shows that the shelf high-Cl− fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.

Alteration of volcanic matter in deep sea sediments: evidence from the chemical composition of interstitial waters from deep sea drilling cores

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.

Lithium isotope geochemistry of pore waters from ocean drilling program Sites 918 and 919, Irminger Basin

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. δ6Li values of pore waters at these two sites vary between −42 and −25 ‰. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of δ6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5–10% of the total inputs from rivers and submarine hot springs.