The Effects of Retrograde Reactions and of Diffusion on 40Ar-39Ar Ages of Micas

The effects of metamorphic reactions occurring during decompression were explored to understand their influence on the 40Ar-39Ar ages of micas. Monometamorphic metasediments from the Lepontine Alps (Switzerland) reached lower amphibolite facies during the Barrovian metamorphism related to the collision between European and African (Adria) continental plates. Mineral assemblages typically composed of garnet, plagioclase, biotite, muscovite and paragonite (or margarite) were screened for petrological equilibrium, to focus on samples that record a minimum degree of retrogression. X-ray diffraction data indicate that some mineral separates prepared for 40Ar-39Ar stepwise heating analysis are monomineralic, whereas others are composed of two white micas (muscovite with paragonite or margarite), or biotite and chlorite. In monomineralic samples 37Ar/39Ar and 38Ar/39Ar (proportional to Ca/K and Cl/K ratios) did not change and the resulting ages can be interpreted unambiguously. In mineral separates containing two white micas, Ca/K and Cl/K ratios were variable, reflecting non-simultaneous laboratory degassing of the two heterochemical Ar reservoirs. These ratios were used to identify each Ar reservoir and to unravel the age. In a chlorite-margarite-biotite calcschist equilibrated near 560°C and 0·65 GPa, biotite, margarite, and muscovite all yield ages around 18 Ma. At slightly higher grade (560-580°C, 0·8-0·9 GPa), the assemblage muscovite-paragonite-plagioclase is in equilibrium and remains stable during retrogression. In this case, muscovite and paragonite yield indistinguishable ages around 16·5 Ma. Above 590°C, paragonite was mostly consumed to form plagioclase >590°C, whereby the relict mica yields an age up to 5·6 Ma younger than muscovite. This partial or total resetting of the Ar clock in paragonite is interpreted to reflect plagioclase growth during decompression. Where biotite is present within this same assemblage, it systematically yields a younger age than muscovite, by 0·5-2 Ma. However, these biotites all show small amounts of retrograde chlorite formation. We conclude that even very minor chloritization of biotite is apparently a more effective process than temperature in resetting the Ar clock, as is the formation of plagioclase from paragonite decomposition. Multi-equilibrium thermobarometry is an excellent means to ensure that equilibrium in investigated samples is preserved, and this helps to obtain geologically meaningful metamorphic ages. However, even samples passing such equilibrium tests may still show retrograde effects that affect the Ar retention of micas. A more robust interpretation of such 40Ar-39Ar results may require use of a second geochronometer, such as U-Pb on monazit

The World's Highest-Grade Cobalt Mineralization at Bou Azzer Associated With Gondwana Supercontinent Breakup, Serpentinite and Kellwasser Hydrocarbon Source Rocks

Cobalt arsenide deposits associated with Neoproterozoic serpentinite in Morocco represent the highest-grade cobalt resource worldwide. Yet, genetic models for their origin remain controversial. We report here mineralogical and geochemical evidence for arsenide-calcite mineralization at Bou Azzer to constrain the temporal framework and identify the geodynamic trigger for mineralization mechanisms. To this end, radiometric ages for ore minerals are paramount for understanding the origin of the Bou Azzer cobalt arsenide deposit. New safflorite (CoAs2) rhenium-osmium (Re-Os) ages are Late Devonian in age: 380.4 ± 2.9 and 373.4 ± 1.2 to 368.1 ± 5.0 million years ago (Ma) for coarse-grained and fine-grained safflorite, respectively. These dates overlap with the timing of break-up of the supercontinent Gondwana, and the building of an arch-and-basin geometry from northern Africa to Arabia. Our findings temporally and spatially contextualize previous knowledge of fluid chemistry and mineralization mechanisms involving a two-fluid mixing. Arsenide mineralization resulted from mixing of a methane-dominated fluid with highly saline basinal brines that leached Os (187Os/188Osinitial = 0.120 ± 0.001), and by corollary cobalt, from Neoproterozoic serpentinite. Carbon and sulfur stable isotope data of ore-stage calcite and arsenides, respectively, show that hydrocarbons acted as the main reductant for mineralization. We speculate that the seawater-derived brines sank into the sedimentary basins adjacent to a carbonate platform with the Bou Azzer serpentinite in its basement in the Late Devonian. In the context of an enhanced geothermal gradient, such brines would have been involved in warm hydrothermal alteration of hydrocarbon source rocks of the local expression of the Kellwasser event in the geological record of present-day Morocco. This warm hydrothermal alteration of hydrocarbon source rocks may have taken place for coarse-grained safflorite mineralization (380.4 ± 2.9 Ma) shortly after ca. 382–381 Ma Lower Kellwasser horizons were deposited, or, for fine-grained safflorite mineralization (373.4 ± 1.2 to 368.1 ± 5.0 Ma) while the Upper Kellwasser horizons of present-day Morocco were being deposited

Multiple openings and competitiveness of forward markets: experimental evidence

We test the competition enhancing effect of selling forward in experimental Cournot duopoly and quadropoly with multiple forward markets. We find that having two forward periods yields competitive outcomes and that the results are very close to the predicted theoretical results for both quantity setting duopolies and quadropolies. Our experiments lend strong support to the hypothesis that forward markets are competition enhancing. We then test a new market that allows for endogenously determined indefinitely many forward periods that only close when sellers coordinate on selling a zero amount in a forward market. We find that the outcomes under an endogenous close rule are also very competitive. These results hold for both duopolies and quadropolies

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

Recycling Argon through Metamorphic Reactions: the Record in Symplectites

The 40Ar/39Ar ages of metamorphic micas that crystallized at high temperatures are commonly interpreted as cooling ages, with grains considered to have lost 40Ar via thermally-driven diffusion into the grain boundary network. Recently reported laser-ablation data suggest that the spatial distribution of Ar in metamorphic micas does not always conform to the patterns predicted by diffusion theory and that despite high metamorphic temperatures, argon was not removed efficiently from the local system during metamorphic evolution. In the Western Gneiss Region (WGR), Norway, felsic gneisses preserve microtextural evidence for the breakdown of phengite to biotite and plagioclase symplectites during near isothermal decompression from c. 20–25 to c. 8–12 kbar at ~700°C. These samples provide an ideal natural laboratory to assess whether the complete replacement of one K-bearing mineral by another at high temperatures completely ‘resets’ the Ar clock, or whether there is some inheritance of 40Ar in the neo-crystallized phase. The timing of the high-temperature portion of the WGR metamorphic cycle has been well constrained in previous studies. However, the timing of cooling following the overprint is still much debated. In-situ laser ablation spot dating in phengite, biotite-plagioclase symplectites and coarser, texturally later biotite yielded 40Ar/39Ar ages that span much of the metamorphic cycle. Together these data show that despite residence at temperatures of ~700°C, Ar is not completely removed by diffusive loss or during metamorphic recrystallization. Instead, Ar released during phengite breakdown appears to be partially reincorporated into the newly crystallizing biotite and plagioclase (or is trapped in fluid inclusions in those phases) within a close system. Our data show that the microtextural and petrographic evolution of the sample being dated provides a critical framework in which local 40Ar recycling can be tracked, thus potentially allowing 40Ar/39Ar dates to be linked more accurately to metamorphic history

Association between weight perception and socioeconomic status among adults in the Seychelles

BACKGROUND: Few studies have examined the association between weight perception and socioeconomic status (SES) in sub-Saharan Africa, and none made this association based on education, occupation and income simultaneously. METHODS: Based on a population-based survey (n = 1255) in the Seychelles, weight and height were measured and self-perception of one's own body weight, education, occupation, and income were assessed by a questionnaire. Individuals were considered to have appropriate weight perception when their self-perceived weight matched their actual body weight. RESULTS: The prevalence of overweight and obesity was 35% and 28%, respectively. Multivariate analysis among overweight/obese persons showed that appropriate weight perception was directly associated with actual weight, education, occupation and income, and that it was more frequent among women than among men. In a model using all three SES indicators together, only education (OR = 2.5; 95% CI: 1.3-4.8) and occupation (OR = 2.3; 95% CI: 1.2-4.5) were independently associated with appropriate perception of being overweight. The OR reached 6.9 [95% CI: 3.4-14.1] when comparing the highest vs. lowest categories of SES based on a score including all SES indicators and 6.1 [95% CI: 3.0-12.1] for a score based on education and occupation. CONCLUSIONS: Appropriately perceiving one's weight as too high was associated with different SES indicators, female sex and being actually overweight. These findings suggest means and targets for clinical and population-based interventions for weight control. Further studies should examine whether these differences in weight perception underlie differences in cognitive skills, healthy weight norms, or body size ideals

Argon redistribution during a metamorphic cycle: Consequences for determining cooling rates

40Ar/39Ar thermochronology is commonly used to constrain the rates and times of cooling in exhumed metamorphic terranes, with ages usually linked to temperature via Dodson's closure temperature (TC) formulation. Whilst many metamorphic 40Ar/39Ar data are consistent with the timing of crystallisation or cooling within a chronological framework defined by other, higher temperature, chronometers, other 40Ar/39Ar data are more difficult to interpret. We report white mica and biotite single grain fusion and laser ablation 40Ar/39Ar ages from felsic gneisses from the Western Gneiss Region, Norway. The rocks record isothermal decompression from peak eclogite-facies conditions (white mica stable) to amphibolite-facies conditions (biotite stable) at c. 700 °C. White mica and biotite yield dispersed single grain fusion dates from 416 to 373 Ma and 437 to 360 Ma respectively. In-situ laser ablation analyses provide a similar range, with white mica spot ages ranging from 424 to 370 Ma and biotite spot ages ranging from 437 to 370 Ma. The dates span the duration of the metamorphic cycle suggested by previous studies, and cannot be reconciled with the results of simple models of Ar loss by diffusion during cooling. Samples that show evidence for different physical processes, such as the chemical breakdown of white mica, partial melting, and fluid ingress, generated different age populations to samples that did not experience or record obvious petrological evidence for these processes. Samples that record significant recrystallization and deformation yielded younger white mica (but older biotite) single grain fusion ages than more pristine samples. Amphibolite-facies gneisses that preserve evidence for significant partial melting generated younger biotite ages than samples that recorded evidence for significant hydration. Our data support other reported observations that high-temperature metamorphic mica 40Ar/39Ar dates cannot be assumed to record the timing of cooling through a specific temperature window. Careful assessment of the petrographic context of the dated minerals and consideration of their post-crystallisation history may provide a more robust insight into whether ‘age’ links to ‘stage’ in a temporally meaningful way