Iron isotope fractionation in subterranean estuaries

Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ⁵⁶Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ⁵⁶Fe values down to −5‰. These low δ⁵⁶Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ⁵⁶Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ⁵⁶Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ⁵⁶Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ⁵⁶Fe values relative to river values.     

A thermodynamic model for Fe–Mg dioctahedral K white micas using data from phase-equilibrium experiments and natural pelitic assemblages

The purpose of this study is to derive a solid-solution model for potassic white micas (KWM) encountered in rocks of various bulk compositions, over a wide range of P-T conditions. A compilation of phengite compositions lead us to propose a seven-thermodynamic-component (muscovite, Fe²⁺-Al-celadonite, Mg-Al-celadonite, annite, phlogopite, pyrophyllite and paragonite) ionic solid-solution model which accounts for the Tschermak, Fe-Mg, di/trioctahedral, pyrophyllitic and paragonitic substitutions observed in nature. A four-site mixing model with symmetric Margules parameters to model the Tschermak substitutions, asymmetric Margules parameters to model the other substitutions, and ideal intersite interaction has been adopted. In contrast to previous models, the relevant thermodynamic data and solid-solution properties are calibrated with independent sets of published experiments conducted for the KMASH, KFASH, KFMASH, and KNASH systems, as well as about 200 natural data involving KWM assemblages. The constraints span a wide range of pressure and temperature conditions (150 to 750 °C, 0.5 to 30 kbar), so that our model does not need to be extrapolated outside the calibration range to be used for P-T thermobarometric purposes. The calculated thermodynamic data are interconsistent with the TWQ thermodynamic database and solid-solution models, including that recently published for chlorites.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

An Early-Cambrian UPb apatite cooling age for the high-temperature regional metamorphism in the Piancó area,Borborema Province (NE Brazil): initial conclusions

The Borborema Province (BP) of northeastern Brazil is a complex crustal assemblage, which has undergone a polycyclic evolution during the Proterozoic. In the Piancó-Alto Br??gida belt, a metamorphosed leucosome vein inserted in amphibolites has a trace element pattern suggesting a T-MORB protolith. Apatites yield a REE pattern indicating growth in equilibrium with garnet, thus pointing to its metamorphic origin. UPb analyses yield an age of 540±5 Ma interpreted as a cooling age following amphibolite facies regional metamorphism associated with granitic emplacement at ca. 580 Ma. The resulting slow cooling rates (ranging from ca. 2.5 to 5 °C Ma^?1) are consistent with underplating of mafic magmas, or crustal thickening caused by nappe stacking, as possible processes governing the metamorphic evolution of the BP. To cite this article: B. Dhuime et al., C. R. Geoscience 335 (2003).     

Asymptotic Analysis and Layer Decomposition for the Couplex Exercise

This document explores the possibilities of multiscale expansions and domain decomposition to solve part of the Couplex 1 exercise. We concentrate on the hydrostatic pressure and show that the slenderness of the domain and the large variations of the Darcy constants allows an analytical approximation which our test reveals to be true to relative errors smaller than 10^–3. The numerical tests are done in 2D with freefem+ and in 3D with freefem3D. Some considerations are also given for Iodine transport.     

The petrologic evolution and pre-eruptive conditions of the rhyolitic Kos Plateau Tuff (Aegean arc)

The Kos Plateau Tuff is a large (>60 km³) and young (160 k.y.) calc-alkaline, high-SiO₂ rhyolitic ignimbrite from the active Kos-Nisyros volcanic center in the Aegean arc (Greece). Combined textural, petrological and geochemical information suggest that (1) the system evolved dominantly by crystal fractionation from (mostly unerupted) more mafic parents, (2) the magma chamber grew over ≥ 250 000 years at shallow depth (～1.5-2.5 kb) and was stored as a H₂O-rich crystalline mush close to its solidus (～670-750°C), (3) the eruption occurred after a reheating event triggered by the intrusion of hydrous mafic magma at the base of the rhyolitic mush. Rare banded pumices indicate that the mafic magma only mingled with a trivial portion of resident crystal-rich rhyolite; most of the mush was remobilized following partial melting of quartz and feldspars induced by advection of heat and volatiles from the underplated, hotter mafic influx.     

Experimental Investigation of Turbulent Momentum Transfer in a Neutral Boundary Layer over a Rough Surface

The turbulent characteristics of the neutral boundary layer developing over rough surfaces are not well predicted with operational weather-forecasting models. The problem is attributed to inadequate mixing-length models, to the anisotropy of the flow and to a lack of controlled experimental data against which to validate numerical studies. Therefore, in order to address directly the modelling difficulties for the development of a neutral boundary layer over rough surfaces, and to investigate the turbulent momentum transfer of such a layer, a set of hydraulic flume experiments were carried out. In the experiments, the mean and turbulent quantities were measured by a particle image velocimetry (PIV) technique. The measured velocity variances and fluxes \({(\overline{{u_{i}^{\prime}}{u_{j}^{\prime}}})}\) in longitudinal vertical planes allowed the vertical and longitudinal gradients (?/?z and ?/?x) of the mean and turbulent quantities (fluxes, variances and third-order moments) to be evaluated and the terms of the evolution equations for ?e/?t, \({\partial \overline{u^{\prime 2}}/\partial t}\), \({\partial \overline{w^{\prime 2}}/\partial t}\) and \({\partial \overline{{u^{\prime}}{w^{\prime}}}/\partial t}\) to be quantified, where e is the turbulent kinetic energy. The results show that the pressure-correlation terms allow the turbulent energy to be transferred equitably from \({\overline{{u^{\prime}}^{2}}}\) to \({\overline{{w^{\prime}}^{2}}}\). It appears that the repartition between the constitutive terms of the budget of e, \({\overline{{u^{\prime}}^{2}}}\), \({\overline{{w^{\prime}}^{2}}}\) and \({\overline{{u^{\prime}}{w^{\prime}}}}\) is not significantly affected by the development of the rough neutral boundary layer. For the whole evolution, the transfers of energy are governed by the same terms that are also very similar to the smooth-wall case. The PIV measurements also allowed the spatial integral scales to be computed directly and to be compared with the dissipative and mixing length scales, which were also computed from the data.