Evolution of fluid flow and carbonate recrystallization rates in deep-sea sediments of the Equatorial Pacific

Fluid flow and carbonate recrystallization rates of deep-sea sediments from eight locations in the Equatorial Eastern Pacific were determined by using δ44/40Ca values of pore water and corresponding sediments. The studied drill sites of IODP Exp. 320/321 are located along a transect of decreasing crustal age and reveal different characteristic pore water depth profiles. The younger sites show an overall isotopic equilibration with the sediment in the upper part of the sedimentary column. In the lower part, the δ44/40Ca of the pore water increases back to seawater-like values at the sediment/basalt interface, forming a bulge-shaped pore water profile. The magnitude of the δ44/40Ca pore water bulge decreases with increasing age of the oceanic crust and sediment cover, resulting in seawater-like δ44/40Ca values throughout the sedimentary column in the oldest Sites U1331 and U1332. These findings indicate a seawater-like fluid input from the underlying crust into the sediment. Thus, after sedimentation, carbonate recrystallization processes start to enrich the pore water in 40Ca, and after a time of carbonate recrystallization and cooling of oceanic crust, a flow of seawater-like fluid starts to move upwards through the sedimentary column, enriching the pore water with 44Ca. We established a carbonate recrystallization and fluid flow model to quantify these processes. Our determined carbonate recrystallization rates between 0.000013e(−t/15.5) and 0.00038e(−t/100.5) and fluid flow rates in the range of 0.42–19 m*Myr−1 indicate that the fluid flow within the investigated sites of IODP Exp. 320/321 depends on the sedimentary composition and location of the specific site, especially the proximity to a recharge or discharge site of a hydrothermal convection cell.

How trustworthy are absolute age data from reprecipitated mineral grains?

<p>Absolute dating of rock deformation is often hampered by the observation that the affected minerals are only partly re-equilibrated with respect to their isotopic composition.</p><p>Generally, three different processes enable mineral grains to adjust isotopically during the deformation event, i.e. volume diffusion, recrystallisation as well as dissolution and reprecipitation.</p><p>The degree to which the crystal structure is affected by these processes is different and thus the extent of isotopic equilibration during these processes generally differs in a way that diffusive element exchange is believed to be the most ineffective and slowest process, whereas re- and neo-crystallization seem to be fast and thorough.</p><p>Fluid-induced dissolution and reprecipitation is a very common mineral reaction mechanism in the solid Earth and as the crystal lattice is intensively reworked during this process, elemental and isotopic exchange between matrix and the newly formed crystal should be facilitated.   </p><p>Commonly, element and isotopic exchange during such mineral reactions is thought to occur via aqueous solutions, but new experimental as well as natural data show that the element transfer during mineral dissolution and reprecipitation can also occur in an amorphous material that forms directly by depolymerization of the crystal lattice.</p><p>Furthermore, precipitation of product minerals occurs directly by repolymerization of the amorphous material at the product surface, hence the entire element and isotopic transfer between reactant and product mineral might not involve equilibration with the intercrystalline transport medium with important consequences for the interpretation of age data from re- and neo-crystallized grains.</p>

Major element and oxygen isotope geochemistry of vapour-phase garnet from the Topopah Spring Tuff at Yucca Mountain, Nevada, USA

Twenty vapour-phase garnets were studied in two samples of the Topopah Spring Tuff of the Paintbrush Group from Yucca Mountain, in southern Nevada. The Miocene-age Topopah Spring Tuff is a 350 m thick, devitrified, moderately to densely welded ash-flow tuff that is zoned compositionally from high-silica rhyolite to latite. During cooling of the tuff, escaping vapour produced lithophysae (former gas cavities) lined with an assemblage of tridymite (commonly inverted to cristobalite or quartz), sanidine and locally, hematite and/or garnet. Vapour-phase topaz and economic deposits associated commonly with topaz-bearing rhyolites (characteristically enriched in F) were not found in the Topopah Spring Tuff at Yucca Mountain. Based on their occurrence only in lithophysae, the garnets are not primary igneous phenocrysts, but rather crystals that grew from a F-poor magmaderived vapour trapped during and after emplacement of the tuff. The garnets are euhedral, vitreous, reddish brown, trapezohedral, as large as 2 mm in diameter and fractured. The garnets also contain inclusions of tridymite. Electron microprobe analyses of the garnets reveal that they are almandinespessartine (48.0 and 47.9 mol.%, respectively), have an average composition of (Fe1.46Mn1.45Mg0.03Ca0.10)(Al1.93Ti0.02)Si3.01O12and are comparatively homogeneous in Fe and Mn concentrations from core to rim. Composited garnets from each sample site have δ18O values of 7.2 and 7.4%. The associated quartz (after tridymite) has δ18O values of 17.4 and 17.6%, values indicative of reaction with later, low-temperature water. Unaltered tridymite from higher in the stratigraphic section has a δ18O of 11.1% which, when coupled with the garnet δ18O values in a quartz-garnet fractionation equation, indicates isotopic equilibration (vapour-phase crystallization) at temperatures of ∼600°C. This high-temperature mineralization, formed during cooling of the tuffs, is distinct from the later and commonly recognized low-temperature stage (generally 50−70°C) of calcite, quartz and opal secondary mineralization, formed from downward-percolating meteoric water, that locally coats fracture footwalls and lithophysal floors.

The status of the Makrotantalon Unit (Andros, Greece) within the structural framework of the Attic-Cycladic Crystalline Belt

This study focuses on the status of the Makrotantalon Unit (Andros, Greece) within the framework of the Cycladic nappe stack. We document unambiguous evidence that this unit has experienced blueschist-facies metamorphism and identify previously unknown lawsonite ± pumpellyite assemblages in glaucophane-free metasediments. The position of the presumed tectonic contact at the base of this unit is vague, but roughly outlined by serpentinites. Only a single outcrop displays a weak angular unconformity with cohesive cataclasites in the footwall. Rb–Sr geochronology was carried out on 11 samples representing various rock types collected within or close to inferred or visible fault zones. Owing to a lack of initial isotopic equilibration and/or subsequent disturbance of the Rb–Sr isotope systematics, isochron relationships are poorly developed or non-existing. In NW Andros, direct dating of distinct displacement events has not been possible, but a lower age limit of ~ 40 Ma for final thrusting is constrained by the new data. Sporadically preserved Cretaceous ages either indicate regional differences in the P–T–d history or a different duration of metamorphic overprinting, which failed to completely eliminate inherited ages. The detachment on the NE coast records a later stage of the structural evolution and accommodates extension-related deformation. Apparent ages of ~ 29–25 Ma for samples from this location are interpreted to constrain the time of a significant deformation increment. On a regional scale, the Makrotantalon Unit can be correlated with the South Evia Blueschist Belt, but assignment to a specific subunit is as yet unconfirmed.

Pyruvate shuttling during rest and exercise before and after endurance training in men

We describe the isotopic exchange of lactate and pyruvate after arm vein infusion of [3-13C]lactate in men during rest and exercise. We tested the hypothesis that working muscle (limb net lactate and pyruvate exchange) is the source of the elevated systemic lactate-to-pyruvate concentration ratio (L/P) during exercise. We also hypothesized that the isotopic equilibration between lactate and pyruvate would decrease in arterial blood as glycolytic flux, as determined by relative exercise intensity, increased. Nine men were studied at rest and during exercise before and after 9 wk of endurance training. Although during exercise arterial pyruvate concentration decreased to below rest values ( P < 0.05), pyruvate net release from working muscle was as large as lactate net release under all exercise conditions. Exogenous (arterial) lactate was the predominant origin of pyruvate released from working muscle. With no significant effect of exercise intensity or training, arterial isotopic equilibration [(IEpyruvate/IElactate)·100%, where IE is isotopic enrichment] decreased significantly ( P < 0.05) from 60 ± 3.1% at rest to an average value of 12 ± 2.7% during exercise, and there were no changes in femoral venous isotopic equilibration. These data show that 1) the isotopic equilibration between lactate and pyruvate in arterial blood decreases significantly during exercise; 2) working muscle is not solely responsible for the decreased arterial isotopic equilibration or elevated arterial L/P occurring during exercise; 3) working muscle releases similar amounts of lactate and pyruvate, the predominant source of the latter being arterial lactate; 4) pyruvate clearance from blood occurs extensively outside of working muscle; and 5) working muscle also releases alanine, but alanine release is an order of magnitude smaller than lactate or pyruvate release. These results portray the complexity of metabolic integration among diverse tissue beds in vivo.

Effects of firn ventilation on isotopic exchange

A new model of isotopic diffusion in the upper few meters of firn tracks the isotopic composition of both the ice matrix and the pore-space vapor through time in two dimensions. Stable isotopes in the vapor phase move through the firn by diffusion along concentration gradients and by advection. Wind-driven ventilation carries atmospheric water vapor into the firn, where it mixes with existing pore-space vapor. Unlike previous models, our model allows disequilibrium between pore-space vapor and the surrounding snow grains. We also calculate the isotopic effects of ventilation-driven sublimation and condensation in the firn. Model predictions of isotopic diffusion in firn compare favorably with existing diffusion models. Model results quantify what other investigators have suggested: isotopic change in the upper few meters is more rapid than can be explained by the Whillans and Grootes (1985) model; isotopic equilibration with atmospheric vapor is an important component of post-depositional isotopic change; and ventilation enhances isotopic exchange by creating regions of relatively rapid sublimation and condensation in the firn.