Re-estimation of argon isotope ratios leading to a revised estimate of the Boltzmann constant

In 2013, NPL, SUERC and Cranfield University published an estimate for the Boltzmann constant [1] based on a measurement of the limiting low-pressure speed of sound in argon gas. Subsequently, an extensive investigation by Yang et al [2] revealed that there was likely to have been an error in the estimate of the molar mass of the argon used in the experiment. Responding to [2], de Podesta et al revised their estimate of the molar mass [3]. The shift in the estimated molar mass, and of the estimate of kB, was large: -2.7 parts in 106, nearly four times the original uncertainty estimate. The work described here was undertaken to understand the cause of this shift and our conclusion is that the original samples were probably contaminated with argon from atmospheric air.
 In this work we have repeated the measurement reported in [1] on the same gas sample that was examined in [2, 3]. However in this work we have used a different technique for sampling the gas that has allowed us to eliminate the possibility of contamination of the argon samples. We have repeated the sampling procedure three times, and examined samples on two mass spectrometers. This procedure confirms the isotopic ratio estimates of Yang et al [2] but with lower uncertainty, particularly in the relative abundance ratio R38:36.
 Our new estimate of the molar mass of the argon used in Isotherm 5 in [1] is 39.947 727(15) g mol-1 which differs by +0.50 parts in 106 from the estimate 39.947 707(28) g mol-1 made in [3]. This new estimate of the molar mass leads to a revised estimate of the Boltzmann constant of kB = 1.380 648 60 (97) × 10−23 J K−1 which differs from the 2014 CODATA value by +0.05 parts in 106.&#13

High-precision 40Ar/39Ar dating of pleistocene tuffs and temporal anchoring of the Matuyama-Brunhes boundary

DFM thanks NERC for continued funding of the Argon Isotope Facility at SUERC and NERC Faciltiies grant IP/1626/0516. PRR thanks the Ann and Gordon Getty Foundation and the U.S. National Science Foundation (grant BCS-0715465) for support of his work. LM was funded by the Marie Curie FP7 Intra-European Fellowship Program for the duration of this project. VCS acknowledges support from the John Fell Fund, University of Oxford.High-precision 40Ar/39Ar ages for a series of proximal tuffs from the Toba super-volcano in Indonesia, and the Bishop Tuff and Lava Creek Tuff B in North America have been obtained. Core from Ocean Drilling Project Site 758 in the eastern equatorial Indian Ocean contains discrete tephra layers that we have geochemically correlated to the Young Toba Tuff (73.7 ± 0.3 ka), Middle Toba Tuff (502 ± 0.7 ka) and two eruptions (OTTA and OTTB) related to the Old Toba Tuff (792.4 ± 0.5 and 785.6 ± 0.7 ka, respectively) (40Ar/39Ar data reported as full external precision, 1 sigma). Within ODP 758 Termination IX is coincident with OTTB and hence this age tightly constrains the transition from Marine Isotope Stage 19–20 for the Indian Ocean. The core also preserves the location of the Australasian tektites, and the Matuyama-Brunhes boundary with Bayesian age-depth models used to determine the ages of these events, c. 784 ka and c. 786 ka, respectively. In North America, the Bishop Tuff (766.6 ± 0.4 ka) and Lava Creek Tuff B (627.0 ± 1.5 ka) have quantifiable stratigraphic relationships to the Matuyama-Brunhes boundary. Linear age-depth extrapolation, allowing for uncertainties associated with potential hiatuses in five different terrestrial sections, defines a geomagnetic reversal age of 789 ± 6 ka. Considering our data with respect to the previously published age data for the Matuyama-Brunhes boundary of Sagnotti et al. (2014), we suggest at the level of temporal resolution currently attainable using radioisotopic dating the last reversal of Earths geomagnetic field was isochronous. An overall Matuyama-Brunhes reversal age of 783.4 ± 0.6 ka is calculated, which allowing for inherent uncertainties in the astronomical dating approach, is indistinguishable from the LR04 stack age (780 ± 5 ka) for the geomagnetic boundary. Our high-precision age is 10 ± 2 ka older than the Matuyama-Brunhes boundary age of 773 ± 1 ka, as reported previously by Channell et al. (2010) for Atlantic Ocean records. As ODP 758 features in the LR04 marine stack, the high-precision 40Ar/39Ar ages determined here, as well as the Matuyama-Brunhes boundary age, can be used as temporally accurate and precise anchors for the Pleistocene time scale.Publisher PDFPeer reviewe

‘Radical interpretations’ preclude the use of climatic wiggle matching for resolution of event timings at the highest levels of attainable precision

An age model (Mark et al., 2017) for ODP 758 and the Matuyama-Brunhes boundary transition and Termination IX in the equatorial Indian Ocean is robust and accurate. No significant magnetic lock-in delay is evident at the depth of the Matuyama-Brunhes boundary and the study highlights that 40Ar/39Ar geochronology is critical for dissection of the Pleistocene at the highest levels of temporal precision and minimal model-dependence. Testing of leads and lags in global-scale climate response requires independently dated timescales to reveal the fine-detail recorded by the various climate archives.PostprintPeer reviewe

Developing the cosmogenic He chronometer

Helium isotopes have found wide use in geoscience research, notably as chronometers of surface exposure. This thesis comprises two distinct components around the theme of cosmogenic He determinations. In the first section (Chapter 3) I test whether cosmogenic 3He can be used to determine short exposure times (<30 ka) in volcanic rocks that are significantly older than the exposure time (~60 Ma). Helium isotopes were measured in olivine, ilmenite and plagioclase from early Tertiary basalts from Isle of Skye, Scotland in order to determine exposure ages. Correction for radiogenic He was made with three different methods. The upper limit of exposure ages are variable, and slightly lower than previously determined by 36Cl (Stone et al. 1998). In the second part of the thesis I report characterisation of the new ThermoScientific HELIX-SFT mass spectrometer then compare performance against the existing MAP 215-50 instrument. The reproducibility of helium isotope determinations using the HELIX-SFT (~0.78%) is significantly better than the MAP 215-50, though not as good as reported elsewhere. The reasons for this are discussed and the potential for further improvements are highlighted

Reconstructing the middle to late Pleistocene explosive eruption histories of Popocatépetl, Iztaccíhuatl and Tláloc-Telapón volcanoes in Central México

The Sierra Nevada Volcanic Range (SNVR), which includes Popocatépetl, Iztaccíhuatl and Tláloc-Telapón volcanoes, has been the source of multiple large explosive eruptions that have dispersed tephra across central México. Several eruptions since 40 ka have previously been described, particularly from Popocatépetl, the southernmost volcano of the range. However, the longer-term eruption history of the SNVR is poorly understood, due to challenges with correlating limited exposures of older pyroclastic sequences, and in discriminating between tephras derived from different sources. Here we describe two extensive exposures located between Popocatépetl and Iztaccíhuatl volcanoes, which provide a more complete and longer-term explosive eruption record of the SNVR: the Nepopualco and Xalitzintla tephra sequences. A detailed tephrostratigraphic survey, together with new 40Ar/39Ar geochronological analyses and glass geochemistry, has permitted the characterization of identified eruption units further leading to the determination of geochemical fields for each volcano and the subsequent discernment of volcanic sources. Our results show that, since the collapse of the Los Pies Cone, which destroyed the Paleo-Iztaccíhuatl edifice at 631 ± 44 ka (2σ), Iztaccíhuatl has produced at least 6 explosive rhyolitic eruptions. After coeval activity with Popocatépetl, between ~600 and ~500 ka, Iztaccíhuatl's explosive activity ceased while Popocatépetl's continued until present day. Popocatépetl has produced at least 27 medium to large explosive eruptions (inferred VEI 4–6), commonly of andesitic to dacitic compositions. Some of these eruptions deposited pumice fallout of &gt;1 m thick in both the Nepopualco and Xalitzintla sequences (e.g. the 339 ± 16 ka [2σ] NT-23/WRT-7 eruption), suggesting that Popocatépetl has produced several eruptions similar in magnitude to the well-known ~14 ka Tutti Frutti Pumice (a VEI 6 eruption with a ~5 km3 tephra volume). The Popocatépetl and Iztaccíhuatl tephras are interbedded with deposits from more distal volcanoes, including some mafic to intermediate products of unknown sources (possibly from nearby monogenetic cones) and tephras related to the late Pleistocene eruptions of Tláloc-Telapón (including the tephra layer produced by the San Valentin Ignimbrite, recently 40Ar/39Ar dated in this study at ~102 ka; 2σ). Our new chemical, stratigraphic and geochronologic investigations of these pyroclastic deposits, predominantly from Popocatépetl and Iztaccíhuatl, provide information on the scale and frequency of medium to large magnitude explosive eruptions over a longer-time period than currently known and that have had potential to disperse tephra across central México since the middle to late Pleistocene. This new data can be used to determine the source of further unknown tephras in the region as well as to better assess the volcanic hazard to the densely populated megalopolis of México City

The squalestatins: decarboxy and 4-deoxy analogues as potent squalene synthase inhibitors

Squalestatins without either the hydroxy group at C-4 or the carboxylic acid at C-3 or C-4 were prepared and evaluated for their ability to inhibit rat liver microsomal squalene synthase (SQS) in vitro. These modifications were well tolerated for compounds with the 4,6-dimethyloctenoate ester at C-6 (S1 series). However in analogues without the C-6 ester (H1 series), removal of the C-4 hydroxy group gave compounds with reduced potency, whereas decarboxylation at C-3 resulted in a dramatic loss of SQS inhibitory activity. In comparison with S1 1, C-4 deoxyS1 3 and C-3 decarboxyS1 10 have shorter in vivo durations of action on the inhibition of hepatic cholesterol biosynthesis in rats. C-4 deoxyS1 3 retains good serum cholesterol-lowering ability in marmosets, while C-3 decarboxyS1 10 showed only a marginal effect even at high dose

The Squalestatins: decarboxy and 4-Deoxy analogues as potent squalene synthase inhibitors

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