Pb diffusion in magnetite: dating magnetite crystallization and the timing of remanent magnetization in banded iron formation

The ferrimagnetic mineral magnetite (Fe3O4) is abundant in banded iron formation (BIFs), and has the potential to provide U—Pb or Pb—Pb age information on these rocks because it incorporates small amounts of U during growth. Combined with age measurements, paleomagnetic studies of BIF magnetites may also yield insight into the history of Earth's magnetic field and its relationship to early evolution of Earth's interior and atmosphere. Reliable magnetite ages utilizing Pb isotopes require knowledge of Pb diffusion in the magnetite structure. For this reason, we undertook an experimental investigation of Pb diffusion in magnetite by diffusing Pb2+ ions into pre-polished slabs of natural magnetite oriented parallel to {001} or {111}. A mixture of PbSO4 and Fe2O3 was used as a surface powder source to supply Pb2+ diffusant at the sample surface and at the same time buffer the oxygen fugacity of the system at magnetite-hematite (MH)—a typical fO2 for banded iron formations (BIFs) due to the common presence of both iron oxides (and where Pb2+ is stable relative to other Pb valence states). Diffusion experiments spanned temperatures of 500–675 °C and durations of 75 to 2035 h. Following each experiment, in-diffused Pb was depth-profiled using Rutherford backscattering spectroscopy (RBS) and Pb diffusivities were calculated from the profiles using an infinite half-space diffusion model. The following diffusion law for Pb2+ in magnetite is based upon 12 independent diffusivity measurements: DPb (m2·s−1) = (9 × 10−17 m2·s−1) exp.(−98,000 J·mol−1)/RT) where the uncertainties in the pre-exponential constant and activation energy are ±6% and ± 15%, respectively. Pb diffusion in magnetite over the temperature range of our study is orders of magnitude slower than projected for other divalent cations based on down-temperature extrapolation of previously measured diffusion laws (e.g., for Mn2+, Fe2+, Co2+, and Ni2+). This finding is encouraging in terms of the potential suitability of magnetite for U—Pb age determinations of BIFs and other magnetite-bearing rocks. Indeed, classical Dodson closure temperatures well above 500 °C are not unrealistic in cases where magnetite crystals having large diffusion domains (e.g., >100 μm in radius) are cooled relatively rapidly (e.g., at 100 °C/MYr). This is of particular significance for paleomagnetic studies, since the Curie temperature of magnetite is 580 °C and therefore the age of magnetization in magnetite-bearing rocks may be directly dated. However, slow cooling of magnetites having small diffusion domains can lead to Pb loss at temperatures of 200 °C or lower. Pb mobilization is evaluated for various time-temperature scenarios that involve both heating and cooling as well as “closed-loop” time-temperature paths. We conclude that U—Pb or Pb—Pb age determinations of BIF magnetites are potentially reliable, but isotopic results should be assessed in concert with knowledge of the thermal history of the host rock and the effective grain size of the magnetites

Li zoning in zircon as a potential geospeedometer and peak temperature indicator

Zircon Li concentrations and δ[superscript 7]Li values may potentially trace crustal recycling because continental and mantle-derived zircons yield distinct values. The usefulness of these differences may depend upon the retentivity of zircon to Li concentrations and isotopic ratios. Given the relatively high Li diffusivities measured by Cherniak and Watson (Contrib Mineral Petrol 160: 383–390, 2010), we sought to discover the scenarios under which Li mobility might be inhibited by charge-compensating cations. Toward this end, we conducted “in” diffusion experiments in which Li depth profiles of synthetic Lu-doped, P-doped, and undoped zircon were determined by nuclear reaction analysis. In separate experiments, Li was ion-implanted at depth within polished natural zircon slabs to form a Gaussian Li concentration profile. Diffusively relaxed concentration profiles were measured after heating the slabs to determine diffusivities. In all experiments, which ranged from 920 to 650 °C, calculated diffusivities are in agreement with a previously established Arrhenius relationship calibrated on trace-element-poor Mud Tank zircon. Our revised Arrhenius relationship that includes both datasets is: D[subscript Li] = 9.60 x 10[superscript -7] exp [-278 ± 8 kJ mol[superscript - 1]/RT] m[superscript 2] s[superscript - 1] We also observed that synthetic sector-zoned zircon exhibits near-step-function Li concentration profiles across sectors that correlate with changes in the rare earth element (REE) and P concentrations. This allowed us to examine how Li diffusion might couple with REE diffusion in a manner different than that described above. In particular, re-heating these grains revealed significant Li migration, but no detectable migration of the rare earth elements. Thus, unlike most elements in zircon which are not mobile at the micrometer scale under most time–temperature paths in the crust, Li zoning, relaxation of zoning, or lack of zoning altogether could be used to reveal time–temperature information. Discrete ~10 μm concentration zones of Li within zircon may be partially preserved at 700 °C for tens to hundreds of years, and at 450 °C for millions of years. In this regard, Li zoning in zircon holds significant potential as a geospeedometer, and in some instances as a qualitative indicator of the maximum temperature experienced by the zircon

Robot companion cats for people at home with dementia: a qualitative case study on companotics

The use of robot companion pets for people in care homes has been extensively studied. The results are largely positive, and suggest that they are valuable in enhancing wellbeing, communication and behavioural aspects. However, there has been little research in people’s own homes, possibly due to the cost and complexity of some of the robot pets currently available. As dementia affects people in different ways, this study explores the effects of a robot cat for people in their own homes, without specifically investigating the effects on a particular symptom. We utilised a case study design to investigate the proposition that various factors influence the impact of a robot cat on the person living with dementia and their carer, including acceptability of the robot pet and acceptance of dementia and its symptoms. The qualitative analysis explores the similarities and differences within the data which were gathered during interviews with people with dementia and their families. This analysis revealed four themes: Distraction, Communication, Acceptance and rejection, and Connecting with the cat and connecting with others. These themes were synthesized into two overarching themes: The effect of the cat on mood and behaviour, and The interaction with the cat. We present the acceptability and impact of the robot cat on symptoms of dementia, with data presented across and within the group of participants. Our analysis suggests that benefits of the robot pet were evident, and although this was a small-scale study, where they were accepted, robot pets provided positive outcomes for the participants and their families

In Defence of Modest Doxasticism About Delusions

Here I reply to the main points raised by the commentators on the arguments put forward in my Delusions and Other Irrational Beliefs (OUP, 2009). My response is aimed at defending a modest doxastic account of clinical delusions, and is articulated in three sections. First, I consider the view that delusions are in-between perceptual and doxastic states, defended by Jacob Hohwy and Vivek Rajan, and the view that delusions are failed attempts at believing or not-quite-beliefs, proposed by Eric Schwitzgebel and Maura Tumulty. Then, I address the relationship between the doxastic account of delusions and the role, nature, and prospects of folk psychology, which is discussed by Dominic Murphy, Keith Frankish, and Maura Tumulty in their contributions. In the final remarks, I turn to the continuity thesis and suggest that, although there are important differences between clinical delusions and non-pathological beliefs, these differences cannot be characterised satisfactorily in epistemic terms. \u

Geometry of River Networks I: Scaling, Fluctuations, and Deviations

This article is the first in a series of three papers investigating the detailed geometry of river networks. Large-scale river networks mark an important class of two-dimensional branching networks, being not only of intrinsic interest but also a pervasive natural phenomenon. In the description of river network structure, scaling laws are uniformly observed. Reported values of scaling exponents vary suggesting that no unique set of scaling exponents exists. To improve this current understanding of scaling in river networks and to provide a fuller description of branching network structure, we report here a theoretical and empirical study of fluctuations about and deviations from scaling. We examine data for continent-scale river networks such as the Mississippi and the Amazon and draw inspiration from a simple model of directed, random networks. We center our investigations on the scaling of the length of sub-basin's dominant stream with its area, a characterization of basin shape known as Hack's law. We generalize this relationship to a joint probability density and show that fluctuations about scaling are substantial. We find strong deviations from scaling at small scales which can be explained by the existence of linear network structure. At intermediate scales, we find slow drifts in exponent values indicating that scaling is only approximately obeyed and that universality remains indeterminate. At large scales, we observe a breakdown in scaling due to decreasing sample space and correlations with overall basin shape. The extent of approximate scaling is significantly restricted by these deviations and will not be improved by increases in network resolution.Comment: 16 pages, 13 figures, Revtex4, submitted to PR

Explaining Evidence Denial as Motivated Pragmatically Rational Epistemic Irrationality

This paper introduces a model for evidence denial that explains this behavior as a manifestation of rationality and it is based on the contention that social values (measurable as utilities) often underwrite these sorts of responses. Moreover, it is contended that the value associated with group membership in particular can override epistemic reason when the expected utility of a belief or belief system is great. However, it is also true that it appears to be the case that it is still possible for such unreasonable believers to reverse this sort of dogmatism and to change their beliefs in a way that is epistemically rational. The conjecture made here is that we should expect this to happen only when the expected utility of the beliefs in question dips below a threshold where the utility value of continued dogmatism and the associated group membership is no longer sufficient to motivate defusing the counter-evidence that tells against such epistemically irrational beliefs

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

Decadal to monthly timescales of magma transfer and reservoir growth at a caldera volcano

International audienceCaldera-forming volcanic eruptions are low-frequency, highimpact events capable of discharging tens to thousands of cubic kilometres of magma explosively on timescales of hours to days, with devastating effects on local and global scales1. Because no such eruption has been monitored during its long build-up phase, the precursor phenomena are not well understood. Geophysical signals obtained during recent episodes of unrest at calderas such as Yellowstone, USA, and Campi Flegrei, Italy, are difficult to interpret, and the conditions necessary for large eruptions are poorly constrained2,3. Here we present a study of pre-eruptive magmatic processes and their timescales using chemically zoned crystals from the 'Minoan' caldera-formingeruption of Santorini volcano,Greece4, which occurred in the late 1600s BC. The results provide insights into how rapidly large silicic systems may pass from a quiescent state to one on the edge of eruption5,6. Despite the large volume of erupted magma4 (40-60 cubic kilometres), and the 18,000-year gestation period between the Minoan eruption and the previous major eruption, most crystals in the Minoan magma record processes that occurred less than about 100 years before the eruption. Recharge of the magma reservoir by large volumes of silicic magma (and some mafic magma) occurred during the century before eruption, and mixing between different silicicmagmabatches was still taking place during the final months. Final assembly of large silicic magma reservoirs may occur on timescales that are geologically very short by comparison with the preceding repose period, with major growth phases immediately before eruption. These observations have implications for the monitoring of long-dormant, but potentially active, caldera systems

An exploration of influences on women’s birthplace decision-making in New Zealand: a mixed methods prospective cohort within the Evaluating Maternity Units study

BACKGROUND: There is worldwide debate surrounding the safety and appropriateness of different birthplaces for well women. One of the primary objectives of the Evaluating Maternity Units prospective cohort study was to compare the clinical outcomes for well women, intending to give birth in either an obstetric-led tertiary hospital or a free-standing midwifery-led primary maternity unit. This paper addresses a secondary aim of the study – to describe and explore the influences on women’s birthplace decision-making in New Zealand, which has a publicly funded, midwifery-led continuity of care maternity system. METHODS: This mixed method study utilised data from the six week postpartum survey and focus groups undertaken in the Christchurch area in New Zealand (2010–2012). Christchurch has a tertiary hospital and four primary maternity units. The survey was completed by 82% of the 702 study participants, who were well, pregnant women booked to give birth in one of these places. All women received midwifery-led continuity of care, regardless of their intended or actual birthplace. RESULTS: Almost all the respondents perceived themselves as the main birthplace decision-makers. Accessing a ‘specialist facility’ was the most important factor for the tertiary hospital group. The primary unit group identified several factors, including ‘closeness to home’, ‘ease of access’, the ‘atmosphere’ of the unit and avoidance of ‘unnecessary intervention’ as important. Both groups believed their chosen birthplace was the right and ‘safe’ place for them. The concept of ‘safety’ was integral and based on the participants’ differing perception of safety in childbirth. CONCLUSIONS: Birthplace is a profoundly important aspect of women’s experience of childbirth. This is the first published study reporting New Zealand women’s perspectives on their birthplace decision-making. The groups’ responses expressed different ideologies about childbirth. The tertiary hospital group identified with the ‘medical model’ of birth, and the primary unit group identified with the ‘midwifery model’ of birth. Research evidence affirming the ‘clinical safety’ of primary units addresses only one aspect of the beliefs influencing women’s birthplace decision-making. In order for more women to give birth at a primary unit other aspects of women’s beliefs need addressing, and much wider socio-political change is required

A Graph Algorithmic Approach to Separate Direct from Indirect Neural Interactions

Network graphs have become a popular tool to represent complex systems composed of many interacting subunits; especially in neuroscience, network graphs are increasingly used to represent and analyze functional interactions between neural sources. Interactions are often reconstructed using pairwise bivariate analyses, overlooking their multivariate nature: it is neglected that investigating the effect of one source on a target necessitates to take all other sources as potential nuisance variables into account; also combinations of sources may act jointly on a given target. Bivariate analyses produce networks that may contain spurious interactions, which reduce the interpretability of the network and its graph metrics. A truly multivariate reconstruction, however, is computationally intractable due to combinatorial explosion in the number of potential interactions. Thus, we have to resort to approximative methods to handle the intractability of multivariate interaction reconstruction, and thereby enable the use of networks in neuroscience. Here, we suggest such an approximative approach in the form of an algorithm that extends fast bivariate interaction reconstruction by identifying potentially spurious interactions post-hoc: the algorithm flags potentially spurious edges, which may then be pruned from the network. This produces a statistically conservative network approximation that is guaranteed to contain non-spurious interactions only. We describe the algorithm and present a reference implementation to test its performance. We discuss the algorithm in relation to other approximative multivariate methods and highlight suitable application scenarios. Our approach is a tractable and data-efficient way of reconstructing approximative networks of multivariate interactions. It is preferable if available data are limited or if fully multivariate approaches are computationally infeasible.Comment: 24 pages, 8 figures, published in PLOS On