Limited fluid-rock interaction at marble-gneiss contacts during Cretaceous granulite-facies metamorphism,Seward Peninsula,Alaska

Stable-isotope profiles show that flat-lying marble units acted as impermeable barriers to upward fluid flow in transitional amphibolite-granulite grade rocks of the Kigluaik Mountains, Seward Peninsula, Alaska. The degree of permeability is related to the composition of the marble. The margin of a thick pure dolomite marble chemically reacted with underlying metasyenite (aH₂O=0.2) to form a 2 cm boundary layer of calcite + forsterite by introduction of SiO₂. No fluid penetrated past this reaction front, although the high temperature of metamorphism (800°C) allowed transport of carbon and oxygen isotopes for an additional 2 cm by diffusion through the solid dolomite. A second marble with a higher silica content underwent more decarbonation, which enhanced porosity and lead to a greater extent of isotope transport (2–3 m) in contact with quartzo-feld-spathic gneiss below. An estimate of total fluid flux across the bottom of this marble layer based on the shape of the isotope profile is 1 cm³/cm² directed down, out of the marble. At two other marble-gneiss contacts steep isotopic gradients coincide with lithologic contacts, indicating very little cross-lithology fluid flow. The extent of diffusional transport of isotopes in the marbles is limited and interpreted as indicating the transient presence of a pore fluid, generated by thermally driven devolatilization reactions. No wholesale pervasive advection of C-O-H fluid occurred across the thick, continuous, marble units near the exposed base of the Kigluaik Group section during the entire regional metamorphic cycle. Activities of pore-fluid species were controlled by internal processes. Movement of volatiles and stable-isotopes between contrasting rock-types was dominantly diffusive. Channelized fluid pathways through the marble units developed during uplift and cooling but were not present during peak metamorphism. Heating of the section occurred by conduction, probably from an underlying magma source, and not by advection of a C-O-H fluid.     

Iron isotope fractionation and atom exchange during sorption of ferrous iron to mineral surfaces

The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al₂O₃), goethite (α-FeOOH), quartz (α-SiO₂), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)_aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)_sorb-Fe(II)_aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ^56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)_aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ^56/54Fe(II)_aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)_aq to be affected by sorption.     

Experimental determination of coexisting iron–titanium oxides in the systems FeTiAlO, FeTiAlMgO, FeTiAlMnO, and FeTiAlMgMnO at 800 and 900°C, 1–4 kbar, and relatively high oxygen fugacity

A synthetic, low-melting rhyolite composition containing TiO₂ and iron oxide, with further separate additions of MgO, MnO, and MgO + MnO, was used in hydrothermal experiments to crystallize Ilm-Hem and Usp-Mt solid solutions at 800 and 900°C under redox conditions slightly below nickel–nickel oxide (NNO) to $\approx 3\,\log_{10} f_{{{\text{O}}_{2}}}A synthetic, low-melting rhyolite composition containing TiO₂ and iron oxide, with further separate additions of MgO, MnO, and MgO + MnO, was used in hydrothermal experiments to crystallize Ilm-Hem and Usp-Mt solid solutions at 800 and 900°C under redox conditions slightly below nickel–nickel oxide (NNO) to units above the NNO oxygen buffer. These experiments provide calibration of the FeTi-oxide thermometer + oxygen barometer at conditions of temperature and oxygen fugacity poorly covered by previous equilibrium experiments. Isotherms for our data in Roozeboom diagrams of projected %usp vs. %ilm show a change in slope at ≈ 60% ilm, consistent with the second-order transition from FeTi-ordered Ilm to FeTi-disordered Ilm-Hem. This feature of the system accounts for some, but not all, of the differences from earlier thermodynamic calibrations of the thermobarometer. In rhyolite containing 1.0 wt.% MgO, 0.8 wt.% MnO, or MgO + MnO, Usp-Mt crystallized with up to 14% of aluminate components, and Ilm-Hem crystallized with up to 13% geikielite component and 17% pyrophanite component. Relative to the FeTiAlO system, these components displace the ferrite components in Usp-Mt, and the hematite component in Ilm-Hem. As a result, projected contents of ulv?spinel and ilmenite are increased. These changes are attributed to increased non-ideality along joins from end-member hematite and magnetite to their respective Mg- and Mn-bearing titanate and aluminate end-members. The compositional shifts are most pronounced in Ilm-Hem in the range Ilm_50–80, a solvus region where the chemical potentials of the hematite and ilmenite components are nearly independent of composition. The solvus gap widens with addition of Mg and even further with Mn. The Bacon–Hirschmann correlation of Mg/Mn in Usp-Mt and coexisting Ilm-Hem is displaced toward increasing Mg/Mn in ilmenite with passage from ordered ilmenite to disordered hematite. Orthopyroxene and biotite crystallized in experiments with added MgO and MgO + MnO; their X _Fe varies with and T consistent with equilibria among ferrosilite, annite, and ferrite components, and the chemical potentials of SiO₂ and orthoclase in the liquid. Experimental equilibration rates increased in the order: Opx < Bt < Ilm-Hem < Usp-Mag.     

Accelerated sediment delivery to continental margins during post-orogenic rebound of mountain ranges

Changes in sediment flux to continental margins are commonly interpreted in terms of tectonic growth of topography or climatic change. Here, we show that variations in sediment yield from orogenic systems, previously considered as resulting from climate change, drainage reorganisation or mantle processes can be explained by intrinsic mechanisms of mountain belt/foreland basin systems naturally evolving during post-orogenic decay. Numerical modelling indicates an increase of sediment flux leaving the orogenic system synchronous with the cessation of deposition in the foreland basin and the transition from late syn- to post-orogenesis. Experiments highlight the importance of lithospheric flexure that causes the post-orogenic isostatic rebound of the foreland basin. Erosion of the rebounding foreland basin combined with continued sediment flux from the thrust wedge drives an acceleration in sediment outflux towards continental margins. Sediment budget records in natural settings such as the Northern Pyrenees or Western European Alps also indicate accelerated post-orogenic sediment delivery to the Bay of Biscay and Rhône Delta respectively. These intrinsic processes that determine sediment yield to continental margins must be accounted for prior to consideration of additional external tectonic or climatic controls.