Effects of fluid-rock interaction on Ar-40/Ar-39 geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

In situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid–rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88–82 and 77–74 Ma, respectively. The younger cores have on average lower B contents (∼36 μg/g) than the older ones (∼43–48 μg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable δ11B values (−18‰ to −10‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ± 1.1 Ma for rims surrounding older cores (82.6 ± 0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar δ11B values (−15‰ to −9‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7–68.8 Ma), yielding an inverse isochron age of 65.0 ± 3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-δ11B fluid (δ11B = +7 ± 4‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks

Development and evolution of detachment faulting along 50 km of the Mid-Atlantic Ridge near 16.5N

This is the accepted manuscript. An edited version of this paper was published by AGU. Copyright 2014 American Geophysical Union.A multifaceted study of the slow-spreading Mid-Atlantic Ridge (MAR) at 16.5ºN provides new insights into detachment faulting and its evolution through time. The survey included regional multibeam bathymetry mapping, high-resolution mapping using AUV Sentry, seafloor imaging using the TowCam system, and an extensive rock-dredging program. At different times, detachment faulting was active along ~50 km of the western flank of the study area, and may have dominated spreading on that flank for the last 5 Ma. Detachment morphologies vary and include a classic corrugated massif, non-corrugated massifs, and back-tilted ridges marking detachment breakaways. High-resolution Sentry data reveal one other detachment morphology; a low-angle, irregular surface in the regional bathymetry is shown to be a finely corrugated detachment surface (corrugation wavelength of only tens of meters and relief of just a few meters). Multi-scale corrugations are observed 2-3 km from the detachment breakaway suggesting that they formed in the brittle layer, perhaps by anastomosing faults. The thin wedge of hanging wall lavas that covers a low-angle (6º) detachment footwall near its termination are intensely faulted and fissured; this deformation may be enhanced by the low-angle of the emerging footwall. Active detachment faulting currently is limited to the western side of the rift valley. Nonetheless, detachment fault morphologies also are present over a large portion of the eastern flank on crust > 2 Ma indicating that within the last 5 Ma parts of the ridge axis have experienced periods of two-sided detachment faulting.This work was supported by the National Science Foundation grant number OCE-1155650

Arc magmas sourced from melange diapirs in subduction zones

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Nature Publishing Group for personal use, not for redistribution. The definitive version was published in Nature Geoscience 5 (2012): 862-867, doi:10.1038/ngeo1634.At subduction zones, crustal material is recycled back into the mantle. A certain proportion, however, is returned to the overriding plate via magmatism. The magmas show a characteristic range of compositions that have been explained by three-component mixing in their source regions: hydrous fluids derived from subducted altered oceanic crust and components derived from the thin sedimentary veneer are added to the depleted peridotite in the mantle beneath the volcanoes. However, currently no uniformly accepted model exists for the physical mechanism that mixes the three components and transports them from the slab to the magma source. Here we present an integrated physico-chemical model of subduction zones that emerges from a review of the combined findings of petrology, modelling, geophysics, and geochemistry: Intensely mixed metamorphic rock formations, so-called mélanges, form along the slab-mantle interface and comprise the characteristic trace-element patterns of subduction-zone magmatic rocks. We consider mélange formation the physical mixing process that is responsible for the geochemical three-component pattern of the magmas. Blobs of low-density mélange material, so-called diapirs, rise buoyantly from the surface of the subducting slab and provide a means of transport for well-mixed materials into the mantle beneath the volcanoes, where they produce melt. Our model provides a consistent framework for the interpretation of geophysical, petrological and geochemical data of subduction zones.H.M. was funded by the J. LamarWorzel Assistant Scientist Fund and the Penzance Endowed Fund in Support of Assistant Scientists. Funding from NSF grant #1119403 (G. Harlow) is acknowledged.2013-05-1

Release of oxidizing fluids in subduction zones recorded by iron isotope zonation in garnet

Subduction zones are key regions of chemical and mass transfer between the Earth’s surface and mantle. During subduction, oxidized material is carried into the mantle and large amounts of water are released due to the breakdown of hydrous minerals such as lawsonite. Dehydration accompanied by the release of oxidizing species may play a key role in controlling redox changes in the subducting slab and overlying mantle wedge. Here we present measurements of oxygen fugacity, using garnet–epidote oxybarometry, together with analyses of the stable iron isotope composition of zoned garnets from Sifnos, Greece. We find that the garnet interiors grew under relatively oxidized conditions whereas garnet rims record more reduced conditions. Garnet δ56Fe increases from core to rim as the system becomes more reduced. Thermodynamic analysis shows that this change from relatively oxidized to more reduced conditions occurred during lawsonite dehydration. We conclude that the garnets maintain a record of progressive dehydration and that the residual mineral assemblages within the slab became more reduced during progressive subduction-zone dehydration. This is consistent with the hypothesis that lawsonite dehydration accompanied by the release of oxidizing species, such as sulfate, plays an important and measurable role in the global redox budget and contributes to sub-arc mantle oxidation in subduction zones

The History, Relevance, and Applications of the Periodic System in Geochemistry

Geochemistry is a discipline in the earth sciences concerned with understanding the chemistry of the Earth and what that chemistry tells us about the processes that control the formation and evolution of Earth materials and the planet itself. The periodic table and the periodic system, as developed by Mendeleev and others in the nineteenth century, are as important in geochemistry as in other areas of chemistry. In fact, systemisation of the myriad of observations that geochemists make is perhaps even more important in this branch of chemistry, given the huge variability in the nature of Earth materials – from the Fe-rich core, through the silicate-dominated mantle and crust, to the volatile-rich ocean and atmosphere. This systemisation started in the eighteenth century, when geochemistry did not yet exist as a separate pursuit in itself. Mineralogy, one of the disciplines that eventually became geochemistry, was central to the discovery of the elements, and nineteenth-century mineralogists played a key role in this endeavour. Early “geochemists” continued this systemisation effort into the twentieth century, particularly highlighted in the career of V.M. Goldschmidt. The focus of the modern discipline of geochemistry has moved well beyond classification, in order to invert the information held in the properties of elements across the periodic table and their distribution across Earth and planetary materials, to learn about the physicochemical processes that shaped the Earth and other planets, on all scales. We illustrate this approach with key examples, those rooted in the patterns inherent in the periodic law as well as those that exploit concepts that only became familiar after Mendeleev, such as stable and radiogenic isotopes

Boron isotope and light element sector zoning in tourmaline: Implications for the formation of B-isotopic signatures

Hourglass sector zoning in metamorphic tourmaline is known to effectively fractionate the major and trace elements between different sectors, producing three distinct compositions at the growth surface. Here we show that the light elements Li, Be, H and B, as well as the δ11B signature are also affected by sector zoning. The sector enrichment in elements is controlled by a dual process of initial preference due to growth surface charge and morphology, followed by consecutive, charge-balance controlled enrichment. The light elements, especially B and H, appear to act as charge-balance cations in this mechanism, with a preferred B3+ for Si4+ and O2- for OH- substitution in the c- sector. A lighter δ11B signature (Δc+c- = 1.8 ± 0.6 ‰) accompanies this increase in BIV in the c- sector, in line with the lighter signatures for BIV compared to BIII in minerals. However, it exceeds this theoretical fractionation by a factor of 10. Although we have not identified a definite process that is responsible for this fractionation, it may be related to local variations in host medium along the growth surface resulting from preferred uptake of elements. These observations show that δ11B signatures in tourmaline are not an independent measure of its host environment, but also a function of mineral composition, and the 3-dimensional zoning variations herein. © 2007 Elsevier B.V. All rights reserved

Fluorapatite-monazite relationships in granulite-facies metapelites, Schwarzwald, southwest Germany

Fluorapatite grains with monazite inclusions and/or rim grains are described in two of four samples from a set of granulite-facies metapelites collected from the Variscan Schwarzwald, southern Germany. Fluorapatite in all four samples appears to have experienced some dissolution in the partial granitic melt formed during granulite-facies metamorphism. Monazite inclusions and rim grains are highly deficient in Th and are presumed to have formed from fluorapatite in association with partial melting during granulite-facies metamorphism. Monazite inclusions range from very small (<1 mm) and very numerous to small (12 mm), sometimes elongated, and less numerous; both types are evenly distributed throughout the fluorapatite grain interior. Monazite rim grains tend to be 110 mm. The formation of monazite inclusions is proposed to be due to dissolution-reprecipitation of the fluorapatite by the aqueous fluids inherent in the granitic melt. We propose that an increase in inclusion size coupled with a decrease in inclusion number is due to Ostwald ripening (interfacial energy reduction), which is greatly facilitated by the presence of an interconnected, fluid-filled porosity in the metasomatized fluorapatite. We further propose that monazite rim grains formed principally during partial dissolution of the fluorapatite in the granitic melt and to a lesser extent by partial dissolution-reprecipitation of the fluorapatite grain rim area allowing for the partial removal of (Y+REE). We conclude that fluorapatite, with monazite inclusions and rim grains, experienced partial dissolution in a H2O-rich peraluminous granitic melt compared to fluorapatite with monazite rim grains and no inclusions which reacted with a similar, relatively less H2O-rich melt. In contrast, monazite-free fluorapatite experienced partial dissolution in a comparatively H2O-poor, subaluminous, possibly peralkaline melt