Controls on lithium concentration and diffusion in zircon

This study was supported by ETH Research Grants ETH-34 15-2 (JS), ETH-14 16-1 (FM) and by Swiss National Science Foundation research grant 200020-153112/1 (NK).Thermal annealing of zircons prior to uranium-lead dating by laser ablation inductively coupled plasma mass spectrometry is a commonly-implemented procedure which improves data accuracy and precision by partially repairing radiation damage from the decay of uranium and thorium. However, it also leads to significantly higher concentrations of lithium in the zircon lattice, which become positively correlated with trivalent yttrium and rare earth elements. Prior to such treatments, zircons typically contain lithium below detection limits (typically <0.55 μg g−1), unless correlated with lanthanum and aluminum (i.e., melt/mineral inclusion tracer elements). This suggests that lithium in zircon is primarily sequestered within inclusions, and is able to permeate the crystal lattice to couple with yttrium and rare earth elements during the thermal annealing procedure. This process occurs 2–3 orders of magnitude faster than diffusion experiments have previously determined, indicating that another diffusion mechanism may apply. A model is proposed, whereby: (i) charge compensation of stoichiometrically over-abundant trivalent cations under water-rich magmatic conditions is likely accomplished by hydrogen, given the incompatibility of lithium in zircon and the abundance of hydrogen. However, (ii) conditions that are high temperature and low pressure (characteristic of both thermal annealing and the syn-eruptive environment), drive silicate melt inclusions to exsolve water, generating a motive force for both hydrogen and lithium from inclusions to permeate the lattice in order to reestablish electrochemical equilibrium between the interior and exterior of the zircon. To test the pressure dependency of lithium migration in the zircon lattice, thermal annealing experiments were performed at 850 °C and 1 bar, 2 kbar and 6 kbar using zircons from the Fish Canyon Tuff. The experiments demonstrate that thermal annealing at 2 and 6 kbar inhibits lithium mobility, with zircons registering lithium concentrations below detection limits similar to controls. The experimental results suggest that lithium concentrations in zircon are vulnerable to rapid perturbation by decompression (concurrent with high temperatures), which further indicate that lithium-in-zircon diffusion data should be interpreted with caution.Publisher PDFPeer reviewe

Forming and preserving aragonite in shear zones: First report of blueschist facies metamorphism in the Jabal Akhdar Dome, Oman Mountains

We report the first occurrence of high-pressure metamorphic aragonite in Precambrian carbonates of the Jabal Akhdar Dome in the Oman Mountains (northern Oman). We propose a model for both its formation at blueschist facies conditions and its subsequent preservation to the surface within the tectonic framework of the Late Cretaceous obduction of the Semail Ophiolite. Aragonite formed at temperature ∼350 °C and pressure ≥0.9 GPa and is preserved within mylonitic shear zones and in stretched-fiber dilational veins where the necessary conditions for its formation and preservation, such as plastic strain accommodation, fluid-enhanced mineralogical reactions, and an anisotropic permeability structure, were preferentially met with respect to the surrounding rock. High-strain structural domains are ideal sites to look for and study prograde and retrograde high-pressure metamorphic histories in deeply subducted and exhumed terrains

Split-grain 40Ar/39Ar dating : integrating temporal and geochemical data from crystal cargoes

NERC is acknowledged for continued funding of AIF at SUERC, East Kilbride. This work was supported by an ETH research grant (ETH-05 13-2) and funds from Swiss National Science Foundation research grants (SNSF 200021-146268 and SNSF 200021-155923/1) and US National Science Grant 1425491.Large sanidine crystals from the Mesa Falls Tuff (MFT), Yellowstone volcanic field, have been split and individually dated via high-precision 40Ar/39Ar geochronology with the undated portions further analysed for major elements, trace elements, Pb and Sr isotopes in the sanidine and trace elements in the melt inclusions. This allows the geochemical and geochronological identity of an individual sanidine to be combined. Our MFT sanidines return a preferred eruption age of 1.3011 ± 0.0015/0.0016 Ma (2-sigma, n = 56, MSWD 0.8, analytical/full external) with a significant component of subtly older (up to ~ 2 Ma) crystals. Combined with recent results (Rivera et al., 2016, Journal of Petrology 57, 9, 1677–1704) our data define a global mean sanidine 40Ar/39Ar age for the MFT of 1.3022 ± 0.0006/0.0008 Ma (2 sigma, analytical/full external) relative to Alder Creek sanidine at 1.1891 Ma and total λ40Ar 5.5305e-10, which gives RACsMFT: 1.09542 ± 0.00050. The ability to couple geochemistry and geochronology from a single grain allows us, for the first time, to evaluate the origin of the subtly older sanidines present in the same pumices as juvenile sanidines. Melt inclusions from all Mesa Falls sanidines represent extremely fractionated melts with low Sr contents (max. 12 ppm, n = 39), and rare earth element patterns which require that they be formed from an A-type magma rather than the preceding subduction-related Eocene volcanism as previously suggested. 87Sr/86Sr from juvenile and subtly older sanidines shows the same range of 0.7073 to 0.7096, illustrating the susceptibility of such low-Sr melts to slight degrees of assimilation. Pb isotopic compositions are more restricted and identical between the juvenile and subtly older sanidines in the Mesa Falls Tuff (207Pb/206Pb 0.900–0.903, 208Pb/206Pb 2.217–2.226, n = 83) and these compositions rule out the underlying Huckleberry Ridge Tuff member B as a potential source for the subtly older sanidine. LA-ICPMS 206Pb/238U dating of Mesa Falls zircons supports no role for the Huckleberry Ridge Tuff. Rather, these subtly older sanidines are interpreted as containing excess mantle-derived Ar. The ability to couple the geochemical and geochronological records within individual sanidine crystals that we demonstrate here has potential to provide new insights for a variety of petrological studies such as diffusional modelling.PostprintPeer reviewe

Garnet petrochronology reveals the lifetime and dynamics of phonolitic magma chambers at Somma-Vesuvius

Somma-Vesuvius is one of the most iconic active volcanoes with historic and archeological records of numerous hazardous eruptions. Petrologic studies of eruptive products provide insights into the evolution of the magma reservoir before eruption. Here, we quantify the duration of shallow crustal storage and document the evolution of phonolitic magmas before major eruptions of Somma-Vesuvius. Garnet uranium-thorium petrochronology suggests progressively shorter pre-eruption residence times throughout the lifetime of the volcano. Residence times mirror the repose intervals between eruptions, implying that distinct phonolite magma batches were present throughout most of the volcano’s evolution, thereby controlling the eruption dynamics by preventing the ascent of mafic magmas from longer-lived and deeper reservoirs. Frequent lower-energy eruptions during the recent history sample this deeper reservoir and suggest that future Plinian eruptions are unlikely without centuries of volcanic quiescence. Crystal residence times from other volcanoes reveal that long-lived deep-seated reservoirs and transient upper crustal magma chambers are common features of subvolcanic plumbing systems

A New Albite Microanalytical Reference Material from Piz Beverin for Na, Al and Si Determination, and the Potential for New K-Feldspar Reference Materials

Determination of alkali elements is important to Earth scientists, yet suitable and reliable microanalytical reference materials are lacking. This paper proposes a new albite reference material and evaluates the potential for future K-feldspar reference materials. The proposed Piz Beverin albite reference material from Switzerland yields a homogeneous composition at the centimetre- to micrometre-scale for Si, Al and Na with \u3c 2000 μg g-1 total trace elements (mostly heterogeneously distributed Ca, K and Sr). EPMA and LA-ICP-MS measurements confirm a composition of 99.5(2)% albite component, which is supported further by bulk XRF measurements. A round robin evaluation involving nine independent EPMA laboratories confirms its composition and homogeneity for Si, Al and Na. In addition, a set of five distinct clear K-feldspar samples was evaluated as possible reference materials. The first two crystals of adular and orthoclase yield unacceptable inhomogeneities with \u3e 2% relative local variations of Na, K and Ba contents. The three other investigated sets of K-feldspar crystals are yellow sanidine crystals from Itrongay (Madagascar). Despite distinct compositions, EPMA confirms they are each homogeneous at the centimetre to micrometre scale for Si, Al and K and have no apparent inclusions; further investigation to find larger amounts of these materials is therefore justified

Microstructural characterization of natural fractures and faults in the Opalinus Clay: insights from a deep drilling campaign across central northern Switzerland

Abstract The Middle-Jurassic Opalinus Clay is the foreseen host rock for radioactive waste disposal in central northern Switzerland. An extensive drilling campaign aiming to characterize the argillaceous formation resulted in a comprehensive drill core data set. The rheologically weak Opalinus Clay is only mildly deformed compared to the over- and underlying rock units but shows a variety of natural fractures. While these structures are hydraulically indistinguishable from macroscopically non-deformed Opalinus Clay today, their analysis allows for a better understanding of the deformation behaviour in the geological past. Here, we present an overview of the different fracture and fault types recorded in the Opalinus Clay and a detailed microstructural characterization of veins—natural dilational fractures healed by secondary calcite and celestite mineralizations. Macroscopic drill core analysis revealed five different natural fracture types that encompass tension gashes of various orientations with respect to bedding and small-scale faults with displacements typically not exceeding the drill core diameter. The occurrence of different fault types generally fits well with the local tectonic setting of the different drilling sites and with respect to the neighbouring regional fault zones. The microstructural investigations of the various vein types revealed their often polyphase character. Fibrous bedding-parallel veins of presumable early age were found to be overprinted by secondary slickenfibres. The polyphase nature of fibrous bedding parallel veins and slickenfibres is supported by differing elemental compositions, pointing towards repeated fracturing and mineralization events. Direct dating of vein calcites with U–Pb was unsuccessful. Nevertheless, age constraints can be inferred from structural orientations and fault slip kinematics. Accordingly, some of the veins already formed during sediment compaction in Mesozoic times, others possibly relate to Early Cenozoic foreland uplift. The youngest veins are most likely related to Late Cenozoic regional tectonic events, such as the Jura fold-and-thrust belt to the south and the Hegau-Lake Constance Graben to the northeast of the study area. During these latest tectonic events, previously formed veins acted as rheologically stiff discontinuities in the otherwise comparably weak Opalinus Clay along which deformation of the rock formation was re-localized

Serpentinization, Carbonation, and Metasomatism of Ultramafic Sequences in the Northern Apennine Ophiolite (NW Italy)

Fluid-rock interaction in ultramafic rocks considerably affects the chemical and isotopic composition of the oceanic lithosphere. We present a geochemical and petrological study of serpentinites and ophicalcites of the Northern Apennine ophiolite, Italy. This ophiolite sequence represents fragments of Jurassic oceanic lithosphere that have been denuded by low angle detachment faults, exposing peridotites on the ocean floor and triggering hydrothermal alteration. Seawater circulation is documented by (Jurassic) seawater-like 87Sr/86Sr values and δ13C values of 1.1–3.0‰ in carbonate veins of the ophicalcites. Bulk rock ophicalcites have low 87Sr/86Sr values of 0.70489–0.70599, elevated SiO2 contents, and talc druses filling calcite veins that record Si-metasomatism. In contrast, underlying serpentinites have 87Sr/86Sr values above Jurassic seawater values. Bulk rock δD and δ18O values of ophicalcites and serpentinites suggest interaction with an evolved seawater-derived and/or magmatic fluid. These chemical signatures result from a complex history of serpentinization, carbonation, and metasomatism. Multiphase water-rock interaction includes infiltration of basement-derived fluids during initial mantle upwelling within an opening ocean basin, followed by localized high-temperature fluid infiltration, extensive seawater circulation resulting in carbonation, and oxidation near the seawater-exposed surface, and finally, fluid-rock interaction with overlying mafic lithologies leading to Si-metasomatism. The studied sequence represents an excellent example of the evolution from serpentinite to ophicalcite during continuous uplift and exposure of ultramafic rocks on the seafloor and documents the complex hydrothermal evolution of ultramafic rocks associated with this process. The extensive chemical transformation of mantle peridotites likely has an impact on geochemical cycles and subduction zone processes

Zircon ages in granulite facies rocks: decoupling from geochemistry above 850 °C?

Granulite facies rocks frequently show a large spread in their zircon ages, the interpretation of which raises questions: Has the isotopic system been disturbed? By what process(es) and conditions did the alteration occur? Can the dates be regarded as real ages, reflecting several growth episodes? Furthermore, under some circumstances of (ultra-)high-temperature metamorphism, decoupling of zircon U–Pb dates from their trace element geochemistry has been reported. Understanding these processes is crucial to help interpret such dates in the context of the P–T history. Our study presents evidence for decoupling in zircon from the highest grade metapelites (> 850 °C) taken along a continuous high-temperature metamorphic field gradient in the Ivrea Zone (NW Italy). These rocks represent a well-characterised segment of Permian lower continental crust with a protracted high-temperature history. Cathodoluminescence images reveal that zircons in the mid-amphibolite facies preserve mainly detrital cores with narrow overgrowths. In the upper amphibolite and granulite facies, preserved detrital cores decrease and metamorphic zircon increases in quantity. Across all samples we document a sequence of four rim generations based on textures. U–Pb dates, Th/U ratios and Ti-in-zircon concentrations show an essentially continuous evolution with increasing metamorphic grade, except in the samples from the granulite facies, which display significant scatter in age and chemistry. We associate the observed decoupling of zircon systematics in high-grade non-metamict zircon with disturbance processes related to differences in behaviour of non-formula elements (i.e. Pb, Th, U, Ti) at high-temperature conditions, notably differences in compatibility within the crystal structure

Food effects on statolith composition of the common cuttlefish (Sepia officinalis)

The concentration of trace elements within cephalopod statoliths can provide a record of the environmental characteristics at the time of calcification. To reconstruct accurately the environmental characteristics at the time of calcification, it is important to understand the influence of as many factors as possible. To test the hypothesis that the elemental composition of cuttlefish statoliths could be influenced by diet, juvenile Sepia officinalis were fed either shrimp Crangon sp. or fish Clupea harengus under equal temperature and salinity regimes in laboratory experiments. Element concentrations in different regions of the statoliths (core–lateral dome–rostrum) were determined using laser ablation inductively coupled plasma mass spectrometry (LA- ICPMS). The ratios of Sr/Ca, Ba/Ca, Mn/Ca and Y/Ca in the statolith’s lateral dome of shrimp-fed cuttlefish were significantly higher than in the statolith’s lateral dome of fish-fed cuttlefish. Moreover, significant differences between statolith regions were found for all analysed elements. The fact that diet adds a considerable variation especially to Sr/Ca and Ba/Ca must be taken into account in future micro-chemical statolith studies targeting cephalopod’s life history