Algorithms and software for U-Pb geochronology by LA-ICPMS

The past 15 years have produced numerous innovations in geochronology, including experimental methods, instrumentation, and software that are revolutionizing the acquisition and application of geochronological data. For example, exciting advances are being driven by Laser-Ablation ICP Mass Spectrometry (LA-ICPMS), which allows for rapid determination of U-Th-Pb ages with 10s of micrometer-scale spatial resolution. This method has become the most commonly applied tool for dating zircons, constraining a host of geological problems. The LA-ICPMS community is now faced with archiving these data with associated analytical results and, more importantly, ensuring that data meet the highest standards for precision and accuracy and that interlaboratory biases are minimized. However, there is little consensus with regard to analytical strategies and data reduction protocols for LA-ICPMS geochronology. The result is systematic interlaboratory bias and both underestimation and overestimation of uncertainties on calculated dates that, in turn, decrease the value of data in repositories such as EarthChem, which archives data and analytical results from participating laboratories. We present free open-source software that implements new algorithms for evaluating and resolving many of these discrepancies. This solution is the result of a collaborative effort to extend the U-Pb_Redux software for the ID-TIMS community to the LA-ICPMS community. Now named ET_Redux, our new software automates the analytical and scientific workflows of data acquisition, statistical filtering, data analysis and interpretation, publication, community-based archiving, and the compilation and comparison of data from different laboratories to support collaborative science

Statistical considerations in high precision U-Pb geochronology, with an application to the tectonic evolution of the North Cascades, Washington

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, 2012.Cataloged from PDF version of thesis.Includes bibliographical references (p. 173-186).The range of geologic problems that may be addressed by U-Pb geochronology is governed by the precision to which U-Pb dates can be measured, expressed as their estimated uncertainties. Accurate and precise knowledge of both the value and uncertainty of an isotopic date are imperative to its correct interpretation. This thesis focuses on quantitatively addressing the large volume of information that contributes to the calculation of published high-precision U-Pb dates. A new algorithm (Chapter 2) outlines the equations that transform measured isotope ratios, along with a host of laboratory and instrumental parameters, into a U-Pb date. The algorithm propagates all known random and systematic uncertainties, resulting in an adaptable framework will remain usable as analytical and computational advances change the main uncertainty contributions. The data reduction and uncertainty propagation algorithm, as well as a new method for calculating weighted means that correctly treats systematic uncertainties, have been incorporated into the open-source software program U-PbRedux. Chapter 3 explores the mechanisms of isotopic fractionation, the largest instrumental correction to measured U-Pb data, using a new linear regression algorithm. The algorithm rapidly regresses a straight line through large datasets in multiple dimensions using a novel simplification to the maximum likelihood objective equation, and is used to demonstrate that Pb undergoes mass-independent fractionation in the source of a thermal ionization mass spectrometer. Chapter 4 addresses the largest source of systematic uncertainty considered when confederating datasets from different labs, the calibration of the tracer used for isotope dilution. The calibration assumes only first-principles mass and purity measurements traceable to SI units, then defines a measurement model that utilizes >105 measurements in a series of overdetermined inverse problems to estimate the tracer isotopic composition. The result is a reduction by a factor of almost four in the tracer uncertainty contribution to a U-Pb date. In Chapter 5, I use the new algorithms to explore regional geology. High-precision U-Pb dates from the metamorphic core of the North Cascades and from ash beds in three fluvial basins that flank it show that Eocene magmatism, solid-state deformation, and exhumation of the metamorphic core are coincident with rapid basin subsidence.by Noah Morgan McLean.Ph.D

Isotopic composition ( 238 U/ 235 U) of some commonly used uranium reference materials

Abstract We have determined 238 U/ 235 U ratios for a suite of commonly used natural (CRM 112a, SRM 950a, and HU-1) and synthetic (IRMM 184 and CRM U500) uranium reference materials by thermal ionisation mass-spectrometry (TIMS) using the IRMM 3636 233 U-236 U double spike to accurately correct for mass fractionation. Total uncertainty on the 238 U/ 235 U determinations is estimated to be <0.02% (2r). These natural 238 U/ 235 U values are different from the widely used 'consensus' value (137.88), with each standard having lower 238 U/ 235 U values by up to 0.08%. The 238 U/ 235 U ratio determined for CRM U500 and IRMM 184 are within error of their certified values; however, the total uncertainty for CRM U500 is substantially reduced (from 0.1% to 0.02%). These reference materials are commonly used to assess mass-spectrometer performance and accuracy, calibrate isotope tracers employed in U, U-Th and U-Pb isotopic studies, and as a reference for terrestrial and meteoritic 238 U/ 235 U variations. These new 238 U/ 235 U values will thus provide greater accuracy and reduced uncertainty for a wide variety of isotopic determinations

Evaluating uncertainties in the calibration of isotopic reference materials and multi-element isotopic tracers (EARTHTIME Tracer Calibration Part II)

A statistical approach to evaluating uncertainties in the calibration of multi-element isotopic tracers has been developed and applied to determining the isotopic composition of mixed U-Pb (202Pb-205Pb-233U-235U) tracers used for accurate isotope dilution U-Pb geochronology. Our experiment, part of the EARTHTIME initiative, directly links the tracer calibration to first-principles measurements of mass and purity that are all traceable to SI units, thereby quantifying the accuracy and precision of U-Pb dates in absolute time. The calibration incorporates new more accurate and precise purity measurements for a number of commonly used Pb and U reference materials, and requires inter-relating their isotopic compositions and uncertainties. Similar methods can be used for other isotope systems that utilize multiple isotopic standards for calibration purposes. We also detail the inter-calibration of three publicly available U-Pb gravimetric solutions, which can be used to bring the same first-principles traceability to in-house U-Pb tracers from other laboratories. Accounting for uncertainty correlations in the tracer isotope ratios yields a tracer calibration contribution to the relative uncertainty of a 206Pb/238U date that is only half of the relative uncertainty in the 235U/205Pb ratio of the tracer, which was historically used to approximate the tracer related uncertainty contribution to 206Pb/238U dates. The tracer uncertainty contribution to 206Pb/238U dates has in this way been reduced to <300 ppm when using the EARTHTIME and similarly calibrated tracers

Zircon U-Pb Geochronology Links the End-Triassic Extinction with the Central Atlantic Magmatic Province

The end-Triassic extinction is characterized by major losses in both terrestrial and marine diversity, setting the stage for dinosaurs to dominate Earth for the next 136 million years. Despite the approximate coincidence between this extinction and flood basalt volcanism, existing geochronologic dates have insufficient resolution to confirm eruptive rates required to induce major climate perturbations. Here, we present new zircon uranium-lead (U-Pb) geochronologic constraints on the age and duration of flood basalt volcanism within the Central Atlantic Magmatic Province. This chronology demonstrates synchroneity between the earliest volcanism and extinction, tests and corroborates the existing astrochronologic time scale, and shows that the release of magma and associated atmospheric flux occurred in four pulses over about 600,000 years, indicating expansive volcanism even as the biologic recovery was under way

Isotopic composition (238U/235U) of some commonly used uranium reference materials

We have determined 238U/235U ratios for a suite of commonly used natural (CRM 112a, SRM 950a, and HU-1) and synthetic (IRMM 184 and CRM U500) uranium reference materials by thermal ionisation mass-spectrometry (TIMS) using the IRMM 3636 233U-236U double spike to accurately correct for mass fractionation. Total uncertainty on the 238U/235U determinations is estimated to be < 0.02% (2σ). These natural 238U/235U values are different from the widely used ‘consensus’ value (137.88), with each standard having lower 238U/235U values by up to 0.08%. The 238U/235U ratio determined for CRM U500 and IRMM 184 are within error of their certified values; however, the total uncertainty for CRM U500 is substantially reduced (from 0.1% to 0.02%). These reference materials are commonly used to assess mass spectrometer performance and accuracy, calibrate isotope tracers employed in U, U-Th and U-Pb isotopic studies, and as a reference for terrestrial and meteoritic 238U/235U variations. These new 238U/235U values will thus provide greater accuracy and reduced uncertainty for a wide variety of isotopic determinations

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb carbonate geochronology: strategies, progress, and limitations

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U–Pb geochronology of carbonate minerals, calcite in particular, is rapidly gaining popularity as an absolute dating method. The high spatial resolution of LA-ICP-MS U–Pb carbonate geochronology has benefits over traditional isotope dilution methods, particularly for diagenetic and hydrothermal calcite, because uranium and lead are heterogeneously distributed on the sub-millimetre scale. At the same time, this can provide limitations to the method, as locating zones of radiogenic lead can be time-consuming and “hit or miss”. Here, we present strategies for dating carbonates with in situ techniques, through imaging and petrographic techniques to data interpretation; our examples are drawn from the dating of fracture-filling calcite, but our discussion is relevant to all carbonate applications. We review several limitations to the method, including open-system behaviour, variable initial-lead compositions, and U–daughter disequilibrium. We also discuss two approaches to data collection: traditional spot analyses guided by petrographic and elemental imaging and image-based dating that utilises LA-ICP-MS elemental and isotopic map data

Protracted timescales of lower crustal growth at the fast-spreading East Pacific Rise

Author Posting. © The Author(s), 2011. 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): 275-278, doi:10.1038/ngeo1378.Formation of the oceanic crust at mid-ocean ridges is a fundamental component of plate tectonics. A majority of the crust at many ridges is composed of plutonic rocks that form by crystallization of mantle-derived magmas within the crust. Recent application of U/Pb dating to samples from in-situ oceanic crust has begun to provide exciting new insight into the timing, duration and distribution of magmatism during formation of the plutonic crust1-4. Previous studies have focused on samples from slow-spreading ridges, however, the time scales and processes of crustal growth are expected to vary with plate spreading rate. Here we present the first high-precision dates from plutonic crust formed at the fast-spreading East Pacific Rise (EPR). Individual zircon minerals yielded dates from 1.420–1.271 million years ago, with uncertainties of ± 0.006–0.081 million years. Within individual samples, zircons record a range of dates of up to ~0.124 million years, consistent with protracted crystallization or assimilation of older zircons from adjacent rocks. The variability in dates is comparable to data from the Vema lithospheric section on the Mid-Atlantic Ridge (MAR)3, suggesting that time scales of magmatic processes in the lower crust may be similar at slow- and fast-spreading ridges.This research was partially funded by NSF grant OCE-0727914 (SAB), a Cardiff University International Collaboration Award (CJL) and NERC grant NE/C509023/1 (CJM).2012-07-2