The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al₂O₃-FeO-Fe₂O₃-MgO-Na₂O-SiO₂-H₂O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f_O2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f_O2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.     

Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles

Sulfur isotope studies of post-Archean terrestrial materials have focused on the ratio ³⁴S/³²S because additional isotopes, ³³S and ³⁶S, were thought to carry little information beyond the well-known mass-dependent relationship among multiple-isotope ratios. We report high-precision analyses of Δ³³S and Δ³⁶S values, defined as deviations of ³³S and ³⁶S from ideal mass-dependent relationships, for international reference materials and sedimentary sulfides of Phanerozoic age by using a fluorination technique with a dual-inlet isotope ratio mass spectrometer. Measured variations in Δ³³S and Δ³⁶S are explained as resulting from processes involve branching reactions (two or more reservoirs formed) or mixing. Irreversible processes in closed systems (Rayleigh distillation) amplify the isotope effect. We outline how this new isotope proxy can be used to gain new insights into fundamental aspects of the sulfur biogeochemical cycle, including additional constraints on seawater sulfate budget and processes in sedimentary sulfide formation. The isotope systematics discussed here cannot explain the much larger variation of Δ³³S and Δ³⁶S observed in Archean rock records. Furthermore, Phanerozoic samples we have studied show a characteristic Δ³³S and Δ³⁶S relationship that differs from those measured in Archean rocks and laboratory photolysis experiments. Thus, high precision analysis of Δ³³S and Δ³⁶S can be used to distinguish small non-zero Δ³³S and Δ³⁶S produced by mass-dependent processes from those produced by mass-independent processes in Archean rocks and extraterrestrial materials.     

Cosmogenic nuclide methods for measuring long-term rates of physical erosion and chemical weathering

Understanding the evolution of geochemical and geomorphic systems requires measurements of long-term rates of physical erosion and chemical weathering. Erosion and weathering rates have traditionally been estimated from measurements of sediment and solute fluxes in streams. However, modern sediment and solute fluxes are often decoupled from long-term rates of erosion and weathering, due to storage or re-mobilization of sediment and solutes upstream from the sampling point. Recently, cosmogenic nuclides such as ¹⁰Be and ²⁶Al have become important new tools for measuring long-term rates of physical erosion and chemical weathering. Cosmogenic nuclides can be used to infer the total denudation flux (the sum of the rates of physical erosion and chemical weathering) in actively eroding terrain. Here we review recent work showing how this total denudation flux can be partitioned into its physical and chemical components, using the enrichment of insoluble tracers (such as Zr) in regolith relative to parent rock. By combining cosmogenic nuclide measurements with the bulk elemental composition of rock and soil, geochemists can measure rates of physical erosion and chemical weathering over 1000- to 10,000-year time scales.     

Effects of Hurricane Ivan on water quality in Pensacola Bay, Florida

Pensacola Bay, Florida, was in the strong northeast quadrant of Hurricane Ivan when it made landfall on September 16, 2004 as a category 3 hurricane on the Saffir-Simpson scale. We present data describing the timeline and maximum height of the storm surge, the extent of flooding of coastal land, and the magnitude of the freshwater inflow pulse that followed the storm. We computed the magnitude of tidal flushing associated with the surge using a tidal prism model. We also evaluated hurricane effects on water quality using water quality surveys conducted 20 and 50 d after the storm, which we compared with a survey 14 d before landfall. We evaluated the scale of hurricane effects relative to normal variability using a 5-yr monthly record. Ivan's 3.5 m storm surge inundated 165 km² of land, increasing the surface area of Pensacola Bay by 50% and its volume by 230%. The model suggests that 60% of the Bay's volume was flushed, initially increasing the average salinity of Bay waters from 23 to 30 and lowering nutrient and chlorophylla concentrations. Additional computations suggest that wind forcing was sufficient to completely mix the water column during the storm. Freshwater discharge from the largest river increased twentyfold during the subsequent 4 d, stimulating a modest phytoplankton bloom (chlorophyll up to 18 μg l⁻¹) and maintaining hypoxia for several months. Although the immediate physical perturbation was extreme, the water quality effects that persisted beyond the first several days were within the normal range of variability for this system. In terms of water quality and phytoplankton productivity effects, this ecosystem appears to be quite resilient in the face of a severe hurricane effect.     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

U–Pb and Hf isotopic analysis of zircon in lower crustal xenoliths from the Navajo volcanic field: 1.4 Ga mafic magmatism and metamorphism beneath the Colorado Plateau

Zircon from lower crustal xenoliths erupted in the Navajo volcanic field was analyzed for U–Pb and Lu–Hf isotopic compositions to characterize the lower crust beneath the Colorado Plateau and to determine whether it was affected by ∼1.4 Ga granitic magmatism and metamorphism that profoundly affected the exposed middle crust of southwestern Laurentia. Igneous zircon in felsic xenoliths crystallized at 1.73 and 1.65 Ga, and igneous zircon in mafic xenoliths crystallized at 1.43 Ga. Most igneous zircon has unradiogenic initial Hf isotopic compositions (ɛ_Hf=+4.1–+7.8) and 1.7–1.6 Ga depleted mantle model ages, consistent with 1.7–1.6 Ga felsic protoliths being derived from “juvenile” Proterozoic crust and 1.4 Ga mafic protoliths having interacted with older crust. Metamorphic zircon grew in four pulses between 1.42 and 1.36 Ga, at least one of which was at granulite facies. Significant variability within and between xenoliths in metamorphic zircon initial Hf isotopic compositions (ɛ_Hf=−0.7 to +13.6) indicates growth from different aged sources with diverse time-integrated Lu/Hf ratios. These results show a strong link between 1.4 Ga mafic magmatism and granulite facies metamorphism in the lower crust and granitic magmatism and metamorphism in the exposed middle crust.