In situ cosmogenic nuclide production rate calibration for the CRONUS-Earth project from Lake Bonneville,Utah, shoreline features

Well-dated bedrock surfaces associated with the highstand and subsequent catastrophic draining of Pleistocene Lake Bonneville, Utah, during the Bonneville flood are excellent locations for in situ cosmogenic nuclide production rate calibration. The CRONUS-Earth project sampled wave-polished bedrock and boulders on an extensive wave-cut bench formed during the Bonneville-level highstand that was abandoned almost instantaneously during the Bonneville flood. CRONUS-Earth also sampled the Tabernacle Hill basalt flow that erupted into Lake Bonneville soon after its stabilization at the Provo level, following the flood. New radiocarbon dating results from tufa at the margins of Tabernacle Hill as part of this study have solidified key aspects of the exposure history at both sites. Both sites have well-constrained exposure histories in which factors such as potential prior exposure, erosion, and shielding are either demonstrably negligible or quantifiable. Multi-nuclide analyses from multiple labs serve as an ad hoc inter-laboratory comparison that supplements and expands on the formalized CRONUS-Earth and CRONUS-EU inter-laboratory comparisons (Blard et al., 2015; Jull et al., 2015; Vermeesch et al., 2015). Results from ¹⁰Be, ²⁶Al, and ¹⁴C all exhibit scatter comparable to that observed in the CRONUS-Earth effort. Although a ³⁶Cl inter-laboratory comparison was not completed for Jull et al. (2015), ³⁶Cl from plagioclase mineral separates exhibits comparable reproducibility. Site production rates derived from these measurements provide valuable input to the global production rate calibration described by Borchers et al. (2015). Whole-rock ³⁶Cl concentrations, however, exhibit inter-laboratory variation exceeding analytical uncertainty and outside the ranges observed for the other nuclides (Jull et al., 2015). A rigorous inter-laboratory comparison studying the systematics of whole-rock ³⁶Cl extraction techniques is currently underway with the goals of delineating the source(s) of this discrepancy and standardizing these procedures going forward.     

Testing the ABOx-SC method: Dating known-age charcoals associated with the Campanian Ignimbrite

Over the past decade several studies have shown the improvements to radiocarbon chronologies that arise when Acid Base Oxidation-Stepped Combustion (ABOx-SC, Bird et al., 1999) pretreatment methods are applied to the dating of charcoal thought to be >30 ka BP. However, few studies have examined whether the use of ABOx-SC produces dates that are not only older, but accurate on known-age charcoal samples that could not be decontaminated using the routine Acid–Base–Acid (ABA) pretreatment protocol. In this study we date 9 charcoal fragments found below the Campanian Ignimbrite (CI) tephra layer, dated by ⁴⁰Ar/³⁹Ar to 39,230 ± 45 years (De Vivo et al., 2001, Rolandi et al., 2003), from three Palaeolithic sites. When treated with the ABOx-SC pretreatment protocol, the radiocarbon dates provide an accurate terminus post quem for the CI. In contrast, the ABA protocol consistently underestimates the age of the tephra. These results serve as a warning against the use of consistency as an indicator for reliability, demonstrate that the routine ABA method is not sufficient to decontaminate charcoal samples from sites of Palaeolithic age, and show that ABOx-SC produces not only older, but accurate age estimates.     

Performance of CRONUS-P – A pyroxene reference material for helium isotope analysis

Helium isotope analyses are central to modern earth science and measured by many noble gas laboratories around the globe (Burnard, 2013; Wieler et al., 2002), spanning a wide spectrum of fundamental research – from identifying primordial reservoirs in the Earth mantle to paleoclimate reconstructions. The CRONUS-Earth initiative included the manufacturing, distribution and analysis of a pyroxene reference material (CRONUS-P) that was designed to be useful for internal reliability control of ³He measurements within a few percent and potentially for ⁴He on a higher level of uncertainty.This short paper describes the CRONUS-P material and its performance as ³He and ⁴He reference sample for noble gas laboratories. The companion paper by Blard et al. 2015 describes in depth the inter-laboratory helium isotope experiment within CRONUS-Earth.We show normalized helium isotope data of CRONUS-P measured at three different noble gas laboratories. Data from all three laboratories show no relation between helium isotope concentrations and sample mass, implying that the material is homogeneous. The data show that CRONUS-P is useful as an internal standard for ³He within better 2% (1σ) and for ⁴He within better 10%.     

40Ar/39Ar dating of the SP and Bar Ten lava flows AZ,USA: Laying the foundation for the SPICE cosmogenic nuclide production-rate calibration project

Precise ⁴⁰Ar/³⁹Ar age determinations made on basalt groundmass collected from the SP and upper and lower Bar Ten lava flows in the San Francisco and Uinkaret volcanic fields of Arizona, USA, yield ages of 72 ± 4, 97 ± 10, and 123 ± 12 ka (2σ; relative to Renne et al., 2010, 2011, full external precision), respectively. Previous ages of the SP lava flow include a K–Ar age of 70 ± 8 ka and OSL ages of 5.5–6 ka. ⁴⁰Ar/³⁹Ar age constraints, relative to the optimization model of Renne et al. (2010, 2011), of 81 ± 50 and 118 ± 64 ka (2σ; full external precision) were previously reported for the upper and lower Bar Ten lava flows, respectively. The new ⁴⁰Ar/³⁹Ar ages are within uncertainty of previous age constraints, and are more robust, accurate, and precise. Preliminary cosmogenic ³He and ²¹Ne production rates from the Bar Ten flows reported by Fenton et al. (2009) are updated here, to account for the improved quality of the ⁴⁰Ar/³⁹Ar data. The new ⁴⁰Ar/³⁹Ar age for the SP flow yields cosmogenic ³He and ²¹Ne production rates for pyroxene (119 ± 8 and 26.8 ± 1.9 at/g/yr; error-weighted mean, 2σ uncertainty; Dunai (2000) scaling method) that are consistent with production rate values reported throughout the literature. The ⁴⁰Ar/³⁹Ar and cosmogenic ³He and ²¹Ne data support field observations indicating the SP flow has undergone negligible erosion. The SP flow contains co-existing phenocrysts of olivine and pyroxene, as well as xenocrysts of quartz in a fine-grained groundmass facilitating cross-calibration of cosmogenic production rates and production-rate (³He, ¹⁰Be, ¹⁴C, ²¹Ne, ²⁶Al, and ³⁶Cl). Thus, we propose the SP flow is an excellent location for a cosmogenic nuclide production-rate calibration site (SPICE: the SP Flow Production-Rate Inter-Calibration Site for Cosmogenic-Nuclide Evaluations).     

The CREp program and the ICE-D production rate calibration database: A fully parameterizable and updated online tool to compute cosmic-ray exposure ages

Over the last decades, cosmogenic exposure dating has permitted major advances in many fields of Earth surface sciences and particularly in paleoglaciology. Yet, exposure age calculation remains a complicated and dense procedure. It requires numerous choices of parameterization and the use of an accurate production rate.This study describes the CREp program (http://crep.crpg.cnrs-nancy.fr) and the ICE-D production rate online database (http://calibration.ice-d.org). This system is designed so that the CREp calculator will automatically reflect the current state of this global calibration database production rate, ICE-D. ICE-D will be regularly updated in order to incorporate new calibration data and reflect the current state of the available literature.CREp is a Octave/Matlab^© online code that computes Cosmic Ray Exposure (CRE) ages for ³He and ¹⁰Be. A stand-alone version of the CREp code is also released with the present article. Note however that only the online version is connected to the online database ICE-D. The CREp program offers the possibility to calculate ages with two scaling models: i.e. the empirical Lal-Stone time-dependent model (Balco et al., 2008; Lal, 1991; Stone, 2000) with the muon parameters of Braucher et al. (2011), and the Lifton-Sato-Dunai (LSD) theoretical model (Lifton et al., 2014). The default atmosphere model is the ERA-40 database (Uppala et al., 2005), but one may also use the standard atmosphere for comparison (N.O.A.A, 1976). To perform the time-dependent correction, users may import their own geomagnetic database for paleomagnetic corrections or opt for one of the three proposed datasets (Lifton, 2016; Lifton et al., 2014; Muscheler et al., 2005).For the important choice of the production rate, CREp is linked to a database of production rate calibration data that is part of the ICE-D (Informal Cosmogenic-nuclide Exposure-age Database) project (http://calibration.ice-d.org). This database includes published empirical calibration rate studies that are publicly available at present, comprising those of the CRONUS-Earth and CRONUS-EU projects, as well as studies from other projects. In the present study, the efficacy of the different scaling models has also been evaluated looking at the statistical dispersion of the computed Sea Level High Latitude (SLHL) production rates. Lal/Stone and LSD models have comparable efficacies, and the impact of the tested atmospheric model and the geomagnetic database is also limited.Users however have several possibilities to select the production rate: 1) using a worldwide mean value, 2) a regionally averaged value (not available in regions with no data), 3) a local unique value, which can be chosen among the existing dataset or imported by the user, or 4) any combination of multiple calibration data.If a global mean is chosen, the 1σ uncertainty arising from the production rate is about 5% for ¹⁰Be and 10% for ³He. If a regional production rate is picked, these uncertainties are potentially lower.CREp is able to calculate a large number of ages in a reasonable time (typically < 30 s for 50 samples). The user may export a summary table of the computed ages and the density probability function associated with each age (in the form of a spreadsheet).     

Reply to Lowe,D.J., Wilson,C.J.N., Newnham,R.M., Hogg,A.G. comment on Grapes, R., Rieser,U., Wang,N., 2010. Optical luminescence dating of a loess section containing a critical tephra marker horizon,SW North Island of New Zealand. Quaternary Geochronology 5, doi:10.1016/j.quageo.2009.01.004, 2010

The arguments presented by Lowe et al. [Lowe, D.J., Wilson, C.J.N., Newham, R.M., Hogg, A.G., 2010. Dating the Kawakawa/Oruanui eruption: comment on “optical luminescence dating of a loess section containing a critical tephra marker horizon, SW North Island of New Zealand” by R. Grapes et al. Quaternary Geochronology 5(4), 493–496] against our IRSL results, which suggested that the widespread Kawakawa tephra (KkT) could be considerably younger than the generally accepted 27.1 ka cal BP age, are unsustainable. We discuss the points raised by Lowe et al., in terms of: 1) Presentation and analysis of luminescence ages (comparison between reporting and error margins of luminescence and ¹⁴C ages, statistical treatment of age data); 2) Possible sources of error (“upbuilding pedogenesis” and its affect on U and Th distribution in loess, effect of biotubation, variation of K in loess, single grain luminescence dating of quartz, probability of luminescence age underestimation in dating tephra); 3) Stratigraphic and paleoenvironmental considerations (ages of tephras overlying KkT, timing of the end of Ohakea loess deposition and its distribution; 4) Radiocarbon-based ages of KkT (problems with the currently accepted ¹⁴C 27.1 ka cal BP age of KkT). We stress that our study was not to establish a new benchmark age for the KkT, but to open debate about the currently accepted benchmark age of the KkT, which we deem to be erroneous.     

An inter-laboratory comparison of cosmogenic 3He and radiogenic 4He in the CRONUS-P pyroxene standard

This study reports an inter-laboratory comparison of the ³He and ⁴He concentrations measured in the pyroxene material CRONUS-P. This forms part of the CRONUS-Earth and CRONUS-EU programs, which also produced a series of natural reference materials for in situ produced ²⁶Al, ¹⁰Be, ¹⁴C, ²¹Ne and ³⁶Cl.Six laboratories (GFZ Potsdam, Caltech Pasadena, CRPG Nancy, SUERC Glasgow, BGC Berkeley, Lamont New York) participated in this intercomparison experiment, analyzing between 5 and 22 aliquots each. Intra-laboratory results yield ³He concentrations that are consistent with the reported analytical uncertainties, which suggests that ³He is homogeneous within CRONUS-P. The inter-laboratory dataset (66 determinations from the 6 different labs) is characterized by a global weighted mean of (5.02 ± 0.12) × 10⁹ at g⁻¹ with an overdispersion of 5.6% (2σ). ⁴He is characterized by a larger variability than ³He, and by an inter-lab global weighted mean of (3.60 ± 0.18) × 10¹³ at g⁻¹ (2σ) with an overdispersion of 10.4% (2σ).There are, however, some systematic differences between the six laboratories. More precisely, 2 laboratories obtained mean ³He concentrations that are about 6% higher than the clustered other 4 laboratories. This systematic bias is larger than the analytical uncertainty and not related to the CRONUS-P material (see Schaefer et al., 2015). Reasons for these inter-laboratory offsets are difficult to identify but are discussed below. To improve the precision of cosmogenic ³He dating, we suggest that future studies presenting cosmogenic ³He results also report the ³He concentration measured in the CRONUS-P material in the lab(s) used in a given study.     

Numerical studies of dispersion due to tidal flow through Moskstraumen, northern Norway

The effect of horizontal grid resolution on the horizontal relative dispersion of particle pairs has been investigated on a short time scale, i.e. one tidal M ₂ cycle. Of particular interest is the tidal effect on dispersion and transports in coastal waters where small-scale flow features are important. A three-dimensional ocean model has been applied to simulate the tidal flow through the Moskstraumen Maelstrom outside Lofoten in northern Norway, well known for its strong current and whirlpools (Gjevik et al., Nature 388(6645):837–838, 1997; Moe et al., Cont Shelf Res 22(3):485–504, 2002). Simulations with spatial resolution down to 50 m have been carried out. Lagrangian tracers were passively advected with the flow, and Lyapunov exponents and power law exponents have been calculated to analyse the separation statistics. It is found that the relative dispersion of particles on a short time scale (12–24 h) is very sensitive to the grid size and that the spatial variability is also very large, ranging from 0 to 100 km² over a distance of 100 m. This means that models for prediction of transport and dispersion of oil spills, fish eggs, sea lice etc. using a single diffusion coefficient will be of limited value, unless the models actually resolves the small-scale eddies of the tidal current.     

Toward the feldspar alternative for cosmogenic 10Be applications

The possibility of quantifying surface processes in mafic or volcanic environment using the potentialities offered by the in situ-produced cosmogenic nuclides, and more specifically by the in situ-produced ¹⁰Be, is often hampered by the rarity of quartz minerals in the available lithologies. As an alternative to overcome this difficulty, we explore in this work the possibility of relying on feldspar minerals rather that on quartz to perform in situ-produced ¹⁰Be measurements in such environments. Our strategy was to cross-calibrate the total production rate of ¹⁰Be in feldspar (P_10fsp) against the total production rate of ³He in pyroxene (P_3px) by measuring ³He and ¹⁰Be in cogenetic pyroxene (³He_px) and feldspar (¹⁰Be_fsp). The samples were collected from eight ignimbritic boulders, exposed from ca 120 to 600 ka at elevations ranging from 800 to 2500 m, along the preserved rock-avalanche deposits of the giant Caquilluco landslide (18°S, 70°W), Southern Peru. Along with data recently published by Blard et al. (2013a) at a close latitude (22°S) but higher elevation (ca. 4000 m), the samples yield a remarkably tight cluster of ³He_px - ¹⁰Be_fsp total production ratios whose weighted-mean is 35.6 ± 0.5 (1σ). The obtained weighted-mean ³He_px - ¹⁰Be_fsp total production ratio combined with the local ³He_py total production rate in the high tropical Andes published by Martin et al. (2017) allows to establish a total SLHL ¹⁰Be in situ-production rate in feldspar mineral (P_10fsp) of 3.57 ± 0.21 at.g⁻¹.yr⁻¹ (scaled for the LSD scaling scheme, the ERA40 atm model and the VDM of Lifton, 2016).Despite the large elevation range covered by the whole dataset (800–4300 m), no significant variation of the ³He_px - ¹⁰Be_fsp total production ratios in pyroxene and feldspar was evidenced. As an attempt to investigate the effect of the chemical composition of feldspar on the total ¹⁰Be production rate, major and trace element concentrations of the studied feldspar samples were analyzed. Unfortunately, giving the low compositional variability of our dataset, this issue is still pending.     

CO<Subscript>2</Subscript> and He degassing at El Chichón volcano,Chiapas, Mexico: gas flux,origin and relationship with local and regional tectonics

During 2007–2008, three CO₂ flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO₂ flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m⁻² day⁻¹ (April 2008) with total emission rates of 164 ± 9.5 (March 2007), 59 ± 2.5 (December 2007) and 109 ± 6.6 t day⁻¹ (April 2008). The mean CO₂ flux estimated from the entire crater floor area was 1,102 g m⁻² day⁻¹ for April 2008 with a total emission rate of 144 ± 5.9 t day⁻¹. Significant change in CO₂ flux was not detected during the period of survey, and the mapping of the CO₂ flux highlighted lineaments reflecting the main local and regional tectonic patterns. The ³He/⁴He ratio (as high as 8.1 R _A) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO₂/³He ratios for the high ³He/⁴He gases tend to have the MORB-like values (1.41 × 10⁹), and the CO₂/³He ratios for the lower ³He/⁴He gases fall within the range for the arc-type gases. The high ³He/⁴He ratios, the MORB-like CO₂/³He ratios for the high ³He/⁴He gases and high proportion of MORB-CO₂ (M = 25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.     

How many and from where? Assessing the sensitivity of exposure durations calculated from paired bedrock 14C/10Be measurements in glacial troughs

We present a sensitivity analysis of the isochron approach of Goehring et al. (2013) for paired measurements of in situ ¹⁴C/¹⁰Be from glacially sculpted bedrock surfaces. This analysis tests how sensitive the resulting exposure durations from this technique are to both the number of samples analyzed and their locations along a glacial trough transect, using a dataset from Goehring et al. (2011) as a test case. A simple equally weighted combinatorial approach was employed to (1) generate non-repetitive combinations of n subsets of samples arranged from the ten possible samples (where n < 10), and (2) estimate the exposure duration and uncertainty for each set of simulations. Results from the Goehring et al. (2011) data indicate that five samples evenly distributed along a transect parallel to the ice margin are the minimum number of samples required for this method, while eight or more samples provide an optimal combination of accuracy and precision at the 1σ level. These findings should be applicable to paired in situ ¹⁴C/¹⁰Be measurements from other polished bedrock troughs at glacial margins, but need further experimental confirmation.     

4He/3He thermochronometry

Using classical diffusion theory, we present a mathematical technique for the determination of ⁴He concentration profiles in minerals. This approach should prove useful for constraining the low-temperature cooling histories of individual samples and for correcting (U–Th)/He ages for partial diffusive loss. The calculation assumes that the mineral of interest contains an artificially produced and uniform distribution of ³He obtained by proton irradiation [Shuster et al., Earth Planet. Sci. Lett. 217 (2004) 19–32]. In minerals devoid of natural helium, this isotope allows measurement of He diffusion coefficients; in minerals with measurable radiogenic He, it permits determination of ⁴He profiles arising during ingrowth and diffusion in nature. The ⁴He profile can be extracted from stepwise degassing experiments in which the ⁴He/³He ratio is measured. The evolution of the ⁴He/³He ratio as a function of cumulative ³He released can be compared with forward models to constrain the shape of the profile. Alternatively, we present a linear inversion that can be used to directly solve for the unknown ⁴He distribution. The inversion incorporates a standard regularization technique to filter the influence of random measurement errors on the solution. Using either approach we show that stepwise degassing data can yield robust and high-resolution information on the ⁴He profile. Profiles of radiogenic He are a sensitive function of the time–Temperate (t–T) path that a cooling sample experienced. Thus, by step heating a proton-irradiated sample it is possible to restrict the sample’s acceptable t–T paths. The sensitivity of this approach was explored by forward-modeling ⁴He profiles resulting from a range of realistic t–T paths, using apatite as an example. Results indicate that ⁴He profiles provide rich information on t–T paths, especially when the profiles are coupled with (U–Th)/He cooling ages on the same sample. Samples that experienced only moderate diffusive loss have ⁴He concentration profiles that are rounded at the edge but uniform in the core of the diffusion domain. Such profiles can be identified by nearly invariant ⁴He/³He ratios after the first few to few tens of percent of ³He have been extracted by step heating. We show how such data can be used to correct (U–Th)/He ages for partial diffusive loss.     

A reevaluation of in situ cosmogenic 3He production rates

³He is among the most commonly measured terrestrial cosmogenic nuclides, but an incomplete understanding of the ³He production rate has limited robust interpretation of cosmogenic ³He concentrations. We use new measurements of cosmogenic ³He in olivine from a well-dated lava flow at Tabernacle Hill, Utah, USA, to calibrate the local ³He production rate. The new ³He measurements (n = 8) show excellent internal consistency and yield a sea level high latitude (SLHL) production rate of 123 ± 4 at g^?1 yr^?1 following the Lal (1991)/Stone (2000) scaling model [Lal, D., 1991. Cosmic ray labeling of erosion surfaces: in situ nuclide production rates and erosion models. Earth and Planetary Science Letters, 104, 424–439.; Stone, J.O., 2000. Air pressure and cosmogenic isotope production. Journal of Geophysical Research, 105, 23753–23759.]. We incorporate the new measurements from Tabernacle Hill in a compilation of all published production rate determinations, characterizing the mean global SLHL production rates (e.g. 120 ± 9.4 at g^?1 yr^?1 with Lal (1991)/Stone (2000)). The internal consistency of the global ³He production rate dataset is as good as the other commonly used cosmogenic nuclides. Additionally, ³He production rates in olivine and pyroxene agree within experimental error. The ³He production rates are implemented in an age and erosion rate calculator, forming a new module of the CRONUS-Earth web-based calculator, a simple platform for cosmogenic nuclide data interpretation [Balco, G., Stone, J., Lifton, N.A., and Dunai, T.J., 2008. A complete and easily accessible means of calculating surface exposure ages or erosion rates from ¹⁰Be and ²⁶Al measurements. Quaternary Geochronology, 3, 174–195.]. The ³He calculator is available online at http://www.cronuscalculators.nmt.edu/.     

Cosmogenic 3He and 21Ne dating of biotite and hornblende

Stable cosmogenic isotopes such as ³He and ²¹Ne are useful for dating of diverse lithologies, quantifying erosion rates and ages of ancient surfaces and sediments, and for assessing complex burial histories. Although many minerals are potentially suitable targets for ³He and ²¹Ne dating, complex production systematics require calibration of each mineral–isotope pair. We present new results from a drill core in a high-elevation ignimbrite surface, which demonstrates that cosmogenic ³He and ²¹Ne can be readily measured in biotite and hornblende. ²¹Ne production rates in hornblende and biotite are similar, and are higher than that in quartz due to production from light elements such as Mg and Al. We measure ²¹Ne_hbl/²¹Ne_qtz = 1.35 ± 0.03 and ²¹Ne_bio/²¹Ne_qtz = 1.3 ± 0.02, which yield production rates of 25.6 ± 3.0 and 24.7 ± 2.9 at g^? 1 yr^? 1 relative to a ²¹Ne_qtz production rate of 19.0 ± 1.8 at g^? 1 yr^? 1. We show that nucleogenic ²¹Ne concentrations produced via the reaction ¹⁸O(α,n)²¹Ne are manageably small in this setting, and we present a new approach to deconvolve nucleogenic ²¹Ne by comparison to nucleogenic ²²Ne produced from the reaction ¹⁹F(α,n)²²Ne in F-rich phases such as biotite. Our results show that hornblende is a suitable target phase for cosmogenic ³He dating, but that ³He is lost from biotite at Earth surface temperatures. Comparison of ³He concentrations in hornblende with previously measured mineral phases such as apatite and zircon provides unambiguous evidence for ³He production via the reaction ⁶Li(n,α)³H → ³He. Due to the atypically high Li content in the hornblende (~ 160 ppm) we estimate that Li-produced ³He represents ~ 40% of total ³He production in our samples, and must be considered on a sample-specific basis if ³He dating in hornblende is to be widely implemented.     

Evaluation of cosmogenic 3He and 21Ne production rates in olivine and pyroxene from two Pleistocene basalt flows,western Grand Canyon,AZ, USA

Combining cosmogenic ³He and ²¹Ne (³He_c and ²¹Ne_c) measurements on both pyroxene and olivine from the Pleistocene Bar Ten flows (85–107 ka) greatly increases our ability to evaluate the accuracy of ³He_c and ²¹Ne_c production rates and, therefore, ³He_c and ²¹Ne_c surface exposure ages. Comparison of ³He_c and ²¹Ne_c age-pairs yielded by experimentally determined production rates and composition-based model calculations indicates that the former give more accurate surface exposure ages than the latter in this study. However, experimental production rates should be adjusted to the composition of the minerals being analyzed to obtain the best agreement between ³He_c and ²¹Ne_c ages for any given sample. ²¹Ne_c/³He_c values are 0.400 ± 0.029 and 0.204 ± 0.014 for olivine and pyroxene, respectively, in Bar Ten lava flows, in agreement with previously published values, and indicate that ²¹Ne_c/³He_c in olivine and pyroxene is not affected by erosion and remains constant with latitude, elevation, and time (up to 10 Myr). Samples with ²¹Ne_c/³He_c that do not agree with these values may indicate the presence of non-cosmogenic helium and/or neon. The neon three-isotope diagram can also indicate whether or not all excess neon in mineral separates comes from cosmogenic sources. An error-weighted regression for olivine defines a spallation line [y = (1.033 ± 0.031)x + (0.09876 ± 0.00033)], which is indistinguishable from that for pyroxene (Schäfer et al., 1999). We have derived a production rate of 25 ± 8 at/g/yr for ²¹Ne_c in clinopyroxene (En_43–44) based on the ⁴⁰Ar/³⁹Ar age of the upper Bar Ten flow. Our study indicates that the production rate of ²¹Ne_c in olivine may be slightly higher than previously determined. Cosmogenic ³He and ²¹Ne remain extremely useful, particularly when paired, in determining accurate eruption ages of young olivine- and pyroxene-rich basaltic lava flows.     

Temporal dissection of the Huckleberry Ridge Tuff using the 40Ar/39Ar dating technique

New high-precision single crystal sanidine ⁴⁰Ar/³⁹Ar ages for the Huckleberry Ridge Tuff (HRT), Yellowstone volcanic field, show that the three HRT members (A, B, and C) represent at least two different eruptions. The new ⁴⁰Ar/³⁹Ar ages (all ages calculated relative to the optimisation model of Renne et al., 2011) are: 2.135 ± 0.006 Ma, 2.131 ± 0.008 Ma, and 2.113 ± 0.004 Ma (2σ, full uncertainty propagation), for members A, B and C, respectively. Members A and B are within uncertainty of one another and both are more precise than, but in agreement with, previously published ages. Member C was erupted later than members A and B. HRT members A and B were deposited during the Reunion Normal Polarity Subchron (C2r.1n). Member C was deposited during Subchron C2r.1r. Previously published radiogenic and stable isotope data show that member C was sourced from an isotopically discrete magma with a higher fraction of crustal material than members A and B. The volume of the first HRT eruption is reduced by c. 12% from previous estimates and explosive eruptions from the Yellowstone volcanic field occurred more frequently, producing more homogeneous magma than was previously believed. High-precision ⁴⁰Ar/³⁹Ar dating is key for resolving the eruptive history of Yellowstone, temporal dissection of voluminous ignimbrites, and rigorous investigation of what constitutes a ‘super-eruption’.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Influence of the crystal field effect on chemical transport in Earth's mantle: Cr3+ and Ga3+ diffusion in periclase

Experiments were performed to determine concentration-dependent diffusion coefficients of Cr³⁺ and Ga³⁺ in periclase at temperatures of 1563–2273 K. Diffusion profiles measured in the quenched samples are consistent with a theoretical model in which the mobile species is a bound M³⁺-vacancy pair, and each profile was fitted to determine the binding energy and diffusion coefficient of the pair. Trivalent chromium-vacancy pairs diffuse more slowly than Ga³⁺-vacancy pairs, and with higher migration energy, 237 kJ/mol vs. 190 kJ/mol. Cation vacancies also bind less tightly to Cr³⁺ than to Ga³⁺, with average binding free energies of ?22 and ?83 kJ/mol, respectively. At all concentrations and temperatures, Cr³⁺ diffuses much more slowly than Ga³⁺, by up to two orders of magnitude. The differences between Cr³⁺ and Ga³⁺ cannot be explained by differences in ionic radius or dipole polarizability, but are consistent with the influence of the crystal field on the partially occupied 3d orbitals of Cr³⁺. The crystal field splitting stabilizes Cr³⁺ on the octahedral cation site, increasing the energy required for Cr³⁺ to exchange positions with an adjacent vacancy. It also makes Cr³⁺-vacancy pairs less favorable, with the presence of a nearest-neighbor vacancy disrupting the symmetry of the octahedral site, thus diminishing the crystal field stabilization. Trends in the diffusion of first-row divalent transition metals in periclase can also be explained by the crystal field effect. High-spin to low-spin transitions in Fe²⁺, Co²⁺ or Mn²⁺ would significantly enhance their crystal field stabilization in periclase, and if such spin transitions occur in the deep mantle, they would be expected to slow the diffusivity of these ions significantly, perhaps by several orders of magnitude.     

High resolution LA-ICP-MS mapping of U and Th isotopes in an early Pleistocene equid tooth from Fuente Nueva-3 (Orce, Andalusia, Spain)

We have produced detailed maps of U and Th isotopes for three cross-sections of an Early Pleistocene equid tooth from the archaeological site of Fuente Nueva-3 (Orce, Andalusia, Spain). This permits us to visualise, for the first time, U migration processes in 3 dimensions. The tooth shows a concentration gradient from the top to the base, indicating the U profile had not equilibrated after >1 Ma. The spatial pattern of ²³⁰Th/²³⁴U and ²³⁴U/²³⁸U indicates complex U-mobilisation processes over the last 100 ka, dominated by small-scale redistribution of U. Leaching from the tooth through the pulp cavity started at least 93 ka ago with several later phases in various domains of the dentine and cement. This leaching event could have been triggered by changes in the local hydrological regime associated with periods of increased erosion in the Guadix-Baza basin. The results illustrate the difficulty of dating faunal material from Early Pleistocene sites. They also demonstrate that dental tissues can neither be considered as homogeneous media for U-diffusion, nor behave as closed systems for U-series isotopes because diagenetic alterations seem to trigger U-migration. The results do not support the notion that U-uptake into dental tissues is necessarily of short duration. Nevertheless, rapid laser ablation scanning can be used to identify suitable samples for dating as well as domains within the teeth that may have preserved original isotopic signatures, i.e. domains that have not been affected by recent U-mobilisation process.