U–Th–Pb zircon geochronology by ID-TIMS, SIMS, and laser ablation ICP-MS: recipes, interpretations, and opportunities

The chronologic record encoded in accessory minerals, based on the radioactive decay of U and Th, is indispensable to extract quantitative process rates over timescales encompassing Earth's evolution from the Hadean to the Holocene, and extending from terrestrial to extra-terrestrial realms. We have essentially three different U–Pb dating tools at hand, a high-precision, whole-grain bulk technique (isotope-dilution thermal ionization mass spectrometry, ID-TIMS), and two high-spatial resolution but less precise in-situ techniques (secondary ion mass spectrometry, SIMS, and laser ablation inductively-coupled plasma mass spectrometry, LA-ICP-MS), all of which are predominantly applied to the mineral zircon. All three have reached a technological and methodological maturity in data quality and quantity, but interpretational differences, which are often common (albeit at different temporal and spatial scales) to all isotopic dating techniques, remain largely unresolved. The choice to use one of these techniques should be governed by the scientific question posed, such as (1) the duration of the geological process to be resolved; (2) the size and abundance of the material to be analyzed; (3) the complexity of the sample material and of the geological history to be resolved; and (4) the number of dates needed to address the question. Our compilation demonstrates that, ultimately, the highest confidence geochronological data will not only result from the optimal choice of appropriate analysis technique and the accurate treatment of analytical and interpretational complexities, but also require comprehensive sample characterization that employs the full gamut of textural (e.g., cathodoluminescence, charge contrast imaging, electron backscatter diffraction) and compositional (e.g., trace element, stable and radiogenic isotope) analysis

The Palaeozoic metamorphic evolution of the Alpine External Massifs

The pre-Mesozoic metamorphic pattern of the External Massifs, composed of subunits of different metamorphic histories, resulted from the telescoping of Variscan, Ordovician and older metamorphic and structural textures and formations. During an early period, the future External Massifs were part of a peri-Gondwanian microplate evolving as an active margin. Precambrian to lower Palaeozoic igneous and sedimentary protoliths were reworked during an Ordovician subduction cycle (eclogites, granulites) preceding Ordovician anatexis and intrusion of Ordovician granitoids. Little is known about the time period when the microcontinent containing the future External Massifs followed a migration path leading to collision with Laurussia. Corresponding rock-series have not been identified. This might be because they have been eroded or transformed by migmatisation or because they remain hidden in the monocyclic areas. Besides the transformations which originated during the Ordovician subduction cycle, strong metamorphic transformations resulted from Variscan collision when many areas underwent amphibolite facies transformations and migmatisation. The different subunits composing the External Massifs and their corresponding P-T evolution are the expression of different levels in a nappe pile, which may have formed before Visean erosion and cooling. The presence of durbachitic magmatic rocks may be the expression of a large scale Early Variscan upwelling line which formed after Variscan lithospheric subduction. Late Variscan wrench fault tectonics and crustal thinning accompanied by high thermal gradients triggered several pulses of granite intrusions

Detection in LA-ICPMS: construction and performance evaluation of decision rules

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) is frequently employed for the analysis of minute isotope contents in the presence of a background noise. Distinguishing between the sample signal and the background noise at a given confidence level thus represents a routine challenge. For count numbers Nb and Ns collected during (equally long) background and sample measurements, respectively, the statistical significance of their net value, Ns, Nb, can be evaluated: how probable is it to obtain such value by subtracting two count number estimates coming from a common statistical distribution (i.e., when Ns and Nb represent measured estimates of the same mean activity)? If, based on the analysis of a model distribution of the net count numbers, we decide that this is probable, the signal is statistically indistinguishable from the background: the analysed isotope is not detected. If the corresponding (one-sided) probability is below some threshold, it is detected. The net signal value on the divide between the above alternatives, given in net counts or mass (content) units, is called critical level; optionally, it can be complemented by the computation of the detection limit; such values are often reported in the literature. Less discussed is the appropriateness of computational methods used to estimate these values. Troubles arise from attempts to apply Gaussian confidence intervals to small, discretely distributed count numbers contained in real LA-ICPMS acquisitions, and from a non-optimal estimation of the net count number standard deviation in some of the methods used for the computation of critical levels for paired measurements. Combined, these factors may result in uncontrolled, excessively high rates of false detections (background reported as detection of analyte in the sample). Here, we provide a review of methods, otherwise called decision rules, available for the critical level estimation and discuss how to evaluate the performances of these rules to enable an educated computation of LA-ICPMS detection capabilities, including the case of small count numbers

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

U-Pb zircon and monazite geochronology of Variscan magmatism related to syn-convergence extension in Central Northern Portugal

The Viseu area is located in the Central Iberian Zone of the Iberian Variscan Belt and hosts numerous post-thickening, collision-related granitoids intruded into upper and middle crustal levels. The present paper reports high precision U-Pb zircon and monazite ages for four plutons of the Viseu area: The syn-kinematic granitoids of Maceira (314±5 Ma), Casal Vasco (311±1 Ma) and Junqueira (307.8±0.7 Ma) and the late-kinematic biotite monzogranites of Cota (306±9 Ma). This points to a synchronous emplacement of the different syn-kinematic plutons shortly followed by the intrusion of the late-kinematic granites and shows that the Upper Carboniferous plutonism occurred within a short time span of ca. 10 million years. The ascent of granite magmas took place after an extensional tectonic event (D2) and is coeval with dextral and sinistral crustal-scale transcurrent shearing (D3). Field and petrographical evidence suggest a narrow time-span between peak T metamorphic conditions and the intrusion of granitic melts which implies very fast uplift rates accommodated through active tectonic exhumation. Magma compositions evolve through time, reflecting an increasing involvement of mid-crustal sources and the underplating effect of an upwelling asthenospheric mantle at the base of a thinning and stretching continental crust. © 2005 Elsevier B.V. All rights reserved

Learning from Sustainability-Oriented Innovation

This chapter argues that insights from the realm of sustainability-oriented innovation can provide useful answers to the question of why Small and Medium-Sized Enterprises (SMEs) would (or should) become interested in implementing responsible innovation practices. It is based on the assumption that “responsible innovation” and “sustainability-oriented innovation” are different approaches aimed at orienting innovation towards increased positive impacts on social and natural environments. Motivations and influences for pursuing sustainability-oriented inno-vation have been studied in the past, and can provide insights into reasons for pursu-ing the implementation of responsible innovation practices

High-precision U–Pb ages in the early Tithonian to early Berriasian and implications for the numerical age of the Jurassic–Cretaceous boundary

The numerical age of the Jurassic–Cretaceous boundary has been controversial and difficult to determine. In this study, we present high-precision U–Pb geochronological data around the Jurassic–Cretaceous boundary in two distinct sections from different sedimentary basins: the Las Loicas, Neuquén Basin, Argentina, and the Mazatepec, Sierra Madre Oriental, Mexico. These two sections contain primary and secondary fossiliferous markers for the boundary as well as interbedded volcanic ash horizons, allowing researchers to obtain new radioisotopic dates in the late Tithonian and early Berriasian. We also present the first age determinations in the early Tithonian and tentatively propose a minimum duration for the stage as a cross-check for our ages in the early Berriasian. Given our radioisotopic ages in the early Tithonian to early Berriasian, we discuss implications for the numerical age of the boundary.</p

Permian high-temperature metamorphism in the Western Alps (NW Italy)

During the late Palaeozoic, lithospheric thinning in part of the Alpine realm caused high-temperature low-to-medium pressure metamorphism and partial melting in the lower crust. Permian metamorphism and magmatism has extensively been recorded and dated in the Central, Eastern, and Southern Alps. However, Permian metamorphic ages in the Western Alps so far are constrained by very few and sparsely distributed data. The present study fills this gap. We present U/Pb ages of metamorphic zircon from several Adria-derived continental units now situated in the Western Alps, defining a range between 286 and 266 Ma. Trace element thermometry yields temperatures of 580-890°C from Ti-in-zircon and 630-850°C from Zr-in-rutile for Permian metamorphic rims. These temperature estimates, together with preserved mineral assemblages (garnet-prismatic sillimanite-biotite-plagioclase-quartz-K-feldspar-rutile), define pervasive upper-amphibolite to granulite facies conditions for Permian metamorphism. U/Pb ages from this study are similar to Permian ages reported for the Ivrea Zone in the Southern Alps and Austroalpine units in the Central and Eastern Alps. Regional comparison across the former Adriatic and European margin reveals a complex pattern of ages reported from late Palaeozoic magmatic and metamorphic rocks (and relics thereof): two late Variscan age groups (~330 and ~300 Ma) are followed seamlessly by a broad range of Permian ages (300-250 Ma). The former are associated with late-orogenic collapse; in samples from this study these are weakly represented. Clearly, dominant is the Permian group, which is related to crustal thinning, hinting to a possible initiation of continental rifting along a passive margin

Seriously personal:The reasons that motivate entrepreneurs to address climate change

This is the author accepted manuscript. The final version is freely available from Springer Verlag via the DOI in this record.Scholars increasingly argue that entrepreneurs and their small- and medium-sized enterprises should play a central role in reducing the rate and magnitude of climate change. However, evidence suggests that while some entrepreneurs recognize their crucial role in addressing climate change, most do not. Why some entrepreneurs nevertheless concern themselves with climate change has largely been overlooked. Some initial work in this area tentatively suggests that these entrepreneurs may engage with climate change because of their personal values, which either focus on financial or socio-ecological reasons, or a combination of both. Yet, it is unclear if all for-profit entrepreneurs engage with climate change for the same reasons, or if indeed their motivations vary across business types. Over a period of four years, we examined entrepreneurs’ motivations to engage with climate change through a variety of qualitative research methods. Our findings illustrate how entrepreneurs who address climate change have motivations specific to their business activity/industry and level of maturity. In each instance, we link these motivations to distinct conceptualizations of time and place. We contend that, through a more differentiated understanding of entrepreneurial motivations, policy-makers can draft climate change-related policies tailored to entrepreneurial needs. Policies could both increase the number of entrepreneurs who already engage in climate change mitigation and leverage the impact of those entrepreneurs already mitigating climate change.This study was funded by the European Social Fund (09099NCO5). We acknowledge with thanks the participation of the entrepreneurs and the support of Business Leaders for Low Carbon, Cornwall Council, and Cornwall Sustainable Tourism Project. The authors wish to thank Professor John Amis, Professor Kenneth Amaeshi and the anonymous reviewers who provided useful feedback on earlier versions of the article