Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Diel Patterns in Chlorophyll <Emphasis Type="Italic">a</Emphasis> Specific Absorption Coefficient and Absorption Efficiency Factor of Picoplankton

Diel patterns in the chlorophyll a specific absorption coefficient of surface picoplankton, a*_pico (γ) (m²·[mg chlorophyll a]⁻¹), were studied at 7 stations under daily cycle of in situ light condition in the western subarctic Pacific and Japan Sea. All the data were normalized by dividing the anomaly with daily averaged a*_pico (γ). Opposite diel patterns were observed for the normalized a*_pico (443) and a*_pico (675) with maximum toward dawn or dusk and minimum toward midday at 4 stations under low-irradiance (LI) conditions and vice versa at 3 stations under high-irradiance (HI) conditions. The absorption efficiency factors at red absorption peak, Q _a (675), were determined by reconstruction with intracellular chlorophyll a concentration and cell diameter. The normalized Q _a (675) also showed diel pattern with maximum toward midday and minimum toward dawn or dusk under LI. The diel pattern in a*_pico (675) and Q _a (675) were primarily caused by changes in intracellular chlorophyll a concentration due to photoadaptation under LI. The diel pattern in a*_pico (443) was influenced by pigmentation, as recognized by blue to red ratio [a*_pico (443)/a*_pico (675)] under HI. This study proposed that the opposite diel pattern in a*_pico (γ) might occur for a wide range of algal species. The results presented here have important consequences for the interpretation of diel variations in optical properties observed in the open ocean.     

CO<Subscript>2</Subscript> Flux Measurements over the Sea Surface by Eddy Correlation and Aerodynamic Techniques

The measurements of the vertical transport of CO₂ were carried out over the Sea of Japan using the specially designed pier of Kyoto University on September 20 to 22, 2000. CO₂ fluxes were measured by the eddy correlation and aerodynamic techniques. Both techniques showed comparable CO₂ fluxes during sea breeze conditions: −0.001 to −0.08 mg m⁻²s⁻¹ with the mean of −0.05 mg m⁻²s⁻¹. This means that the measuring site satisfies the fetch requirement for meteorological observations under sea breeze conditions. Moreover, the eddy diffusivity coefficient used in the aerodynamic technique is found to be consistent with the coefficient used in the eddy correlation technique. The present result leads us to conclude that the aerodynamic technique may be applicable to underway CO₂ flux measurements over the ocean and may be used in place of the bulk technique. The important point is the need to maintain a measuring accuracy of CO₂ concentration difference of the order of 0.1 ppmv on the research vessels or the buoys.     

Seasonal and Spatial Variations of Total Mass Flux around Coral Reefs in the Southern Ryukyus,Japan

Total mass flux, size distribution of sediment particles and some chemical components such as total carbon (TC), total nitrogen (TN) and calcium carbonate (CaCO₃) were monitored monthly using a multi-cup sediment traps at seven coral reef sites (6 reef flat and 1 reef slope) of the Marine Protected Areas around Ishigaki, Kohama, Kuroshima and Iriomote Islands in the southern Ryukyus, Japan from September 2000 to September 2001. The size distribution of trapped sediments revealed mostly uni-modal fine sand to mud in the reef flat and gravelly to coarse sand in the reef slope. The total mass flux ranged between 0.54 to 872 gm⁻²d⁻¹, and showed a pronounced seasonality (high in summer-autumn and low in spring) at each site, which was consistent with the rainfall and typhoon regime. Exceptionally high values were observed on the reef slope (Iriomote) in February–March 2001 (1533 gm⁻²d⁻¹) owing to a large amount of bottom sediment re-suspension. On the reef flat (Todoroki South and North; Ishigaki), values obtained in July–August 2001 (872 gm⁻²d⁻¹) and August–September 2001 (800 gm^{− 2}d⁻¹) indicate the high terrestrial discharge from Todoroki River. Trapped sediment particles consist of CaCO₃ (1.2–27.1%) and a non-carbonate fraction (98.8–72.9%), which contains total carbon (4.9–26%), carbonate carbon (CO₂-C) (0.2–3.1%) and non-carbonate carbon (NC-C) (7.9–25.6%). Total nitrogen content was in the range 0.02–0.48%. TN is contained mainly in the carbonate fraction and NC-C may be contained in the non-carbonate fraction. The low TN/OC ratio of the trapped sediments suggests that they were mostly of terrestrial origin and that both fractions migrated. The high total mass flux derived from Todoroki River exceeded the threshold at which a lethal effect on coral community is caused. The results stress the importance of conducting seasonal studies of sedimentation over more than one year and at more than one location in south Japan coral reef ecosystems to gain an understanding of the processes controlling the total mass fluxes and their nutrients content, also to develop an awareness of how to prevent the damage of coral reef ecosystems and, if it does occur, to allow mitigation measures to be undertaken.     

Seismic structure and tectonics of the Shackleton Fracture Zone (Drake Passage,Scotia Sea)

The structural framework of the southern part of the Shackleton Fracture Zone has been investigated through the analysis of a 130-km-long multichannel seismic reflection profile acquired orthogonally to the fracture zone near 60° S. The Shackleton Fracture Zone is a 800-km-long, mostly rectilinear and pronounced bathymetric lineation joining the westernmost South Scotia Ridge to southern South America south of Cape Horn, separating the western Scotia Sea plate from the Antarctic plate. Conventional processing applied to the seismic data outlines the main structures of the Shackleton Fracture Zone, but only the use of enhanced techniques, such as accurate velocity analyses and pre-stack depth migration, provides a good definition of the acoustic basement and the architecture of the sedimentary sequences. In particular, a strong and mostly continuous reflector found at about 8.0 s two-way traveltime is very clear across the entire section and is interpreted as the Moho discontinuity. Data show a complex system of troughs developed along the eastern flank of the crustal ridge, containing tilted and rotated blocks, and the presence of a prominent listric normal fault developed within the oceanic crust. Positive flower structures developed within the oceanic basement indicate strike-slip tectonism and partial reactivation of pre-existing faults. Present-day tectonic activity is found mostly in correspondence to the relief, whereas fault-induced deformation is negligible across the entire trough system. This indicates that the E–W-directed stress regime present in the Drake Passage region is mainly dissipated along a narrow zone within the Shackleton Ridge axis. A reappraisal of all available magnetic anomaly identifications in the western Scotia Sea and in the former Phoenix plate, in conjunction with new magnetic profiles acquired to the east of the Shackleton Fracture Zone off the Tierra del Fuego continental margin, has allowed us to propose a simple reconstruction of Shackleton Fracture Zone development in the general context of the Drake Passage opening.     

Scaling analysis of deposition from turbidity currents

Many oil-bearing sedimentary deposits are formed by the settling of particles from turbidity currents. Modeling sedimentary processes that form these turbidites enables the calculation of properties such as extent, depth, porosity and permeability of hydrocarbon-bearing reservoirs. This paper estimates the extent and thickness of turbidites from the initial conditions of the turbidity flow. This is achieved by the application of scaling analysis of the partial differential equations that govern the dynamics of and deposition from turbidity currents. We apply the results of scaling analysis to five modern submarine fans. The predicted and actual values of the dimensions of the fan deposits match well. We then compare the derived results against tabulated sizes of ancient turbidites. The comparisons are good as long as we correctly identify the flow regimes in which the deposition took place. The good agreements observed in the two cases show that the estimates obtained using scaling analysis can provide useful first-guess values for the dimensions of the deposits.     

Simple determination of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) using solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r ² > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.     

Syntectonic Mobility of Supergene Nickel Ores of New Caledonia (Southwest Pacific). Evidence from Garnierite Veins and Faulted Regolith

Supergene nickel deposits of New Caledonia that have been formed in the Neogene by weathering of obducted ultramafic rocks are controlled by fracture development. The relationship of tropical weathering and tectonic structures, faults and tension gashes, have been investigated in order to determine whether fractures play a passive role only, as previously thought; or alternatively, if brittle tectonics was acting together with alteration. Observation of time‐relationship, textures, and mineralogy of various fracture fills and fault gouges shows that active faulting has played a prominent role not only in facilitating drainage and providing room for synkinematic crystallization of supergene nickel silicate, but also in mobilizing already formed sparse nickel ore, producing the very high grade ore nicknamed “green gold”.     

The P-T-fO 2 stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10

New equilibrium experiments have been performed in the 20–27 kbar range to determine the upper thermal stability limit of endmember deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. In this pressure range, the maximum thermal stability limit is represented by the oxygen-conserving reaction: deerite(De)=9 ferrosilite(Fs)+3 magnetite(Mag)+3 quartz(Qtz)+5 H₂O(W) (1). Under the oxygen fugacities of the Ni-NiO buffer the breakdown-reduction reaction: De=12 Fs+2 Mag+5 W+1/2 O₂ (10) takes place at lower temperatures (e.g. T=63° at 27 kbar). The experimental brackets can be fitted using thermodynamic data for ferrosilite, magnetite and quartz from Berman (1988) and the following 1 bar, 298 K data for deerite (per gfw): V^o=55.74 J.bar^-1, S^o=1670 J.K^-1, H _f ^o =-18334 kJ, =2.5x10^-5K^-1, =-0.18x10^-5 bar^-1. Using these data in conjunction with literature data on coesite, grunerite, minnesotaite, and greenalite, the P-T stability field of endmember deerite has been calculated for P _s=P _{H 2}O. This field is limited by 6 univariant oxygenconserving dehydration curves, from which three have positive dP/dT slopes, the other three negative slopes. The lower pressure end of the stability field of endmember deerite is thus located at an invariant point at 250±70°C and 10+-1.5 kbar. Deerite rich in the endmember can thus appear only in environments with geothermal gradients lower than 10°C/km and at pressures higher than about 10 kbar, which is in agreement with 4 out of 5 independent P-T estimates for known occurrences. The presence of such deerite places good constraints on minimum pressure and maximum temperature conditions. From log f _{O 2}-T diagrams constructed with the same data base at different pressures, it appears that endmember deerite is, at temperatures near those of its upper stability limit, stable only over a narrow range of oxygen fugacities within the magnetite field. With decreasing temperatures, deerite becomes stable towards slightly higher oxygen fugacities but reaches the hematite field only at temperatures more than 200°C lower than the upper stability limit. This practically precludes the coexistence deerite-hematite with near-endmember deerite in natural environments.