Leah E. Morgan

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved, and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41K to 39K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41K/39K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2σ, N = 108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings. Although our average bulk-silicate Earth value (−0.54‰) is indistinguishable from previously published values, we find systematic δ41K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ41K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems.

40Ar/39Ar geochronology and petrogenesis of the Table Mountain Shoshonite, Golden, Colorado, U.S.A.

&NA; The Upper Cretaceous and Lower Paleogene Table Mountain Shoshonite lava flows and their proposed source, the Ralston Buttes intrusions, provide insight into the volcanic history of the Colorado Front Range. This study affirms the long‐held hypothesis linking the extrusive Table Mountain lava flows and their intrusive equivalents at Ralston Buttes through major‐ and trace‐ element geochemistry. Systematic 40Ar/39Ar geochronology from all flows and intrusive units refines the eruptive history, improves precision on previously reported ages, and provides tighter constraints on the position of the K‐Pg boundary in this location. Four flows are recognized on North and South Table mountains outside of Golden, Colorado. Flow 1 (66.5 ± 0.3 Ma, all ages reported with 2&sgr; uncertainty) is the oldest, most compositionally distinct flow and is separated from younger flows by approximately 35 m of sedimentary deposits of the Denver Formation. Stratigraphically adjacent flows 2 (65.8 ± 0.2 Ma), 3 (65.5 ± 0.3 Ma), and 4 (65.9 ± 0.3 Ma) are compositionally indistinguishable. Lavas (referred to here as unit 5) that form three cone‐shaped structures (shown by this study to be volcanic vents of a new unit 5) on top of North Table Mountain are compositionally similar to other units, but yield an age almost 20 m.y. younger (46.94 ± 0.15 Ma). Geochemistry and geochronology suggest that the rim phase of the Ralston plug (65.4 ± 0.2 Ma) is a reasonable source for flows 2, 3, and 4. All units are shoshonites—potassic basalts containing plagioclase, augite, olivine, and magnetite phenocrysts—and plot in the continental‐arc field in tectonic discrimination diagrams. A continental‐arc setting coupled with Late Cretaceous to early Paleogene ages suggest the high‐K magmatism is associated with Laramide tectonism.

Pressure disequilibria induced by rapid valve closure in noble gas extraction lines

Pressure disequilibria during rapid valve closures can affect calculated molar quantities for a range of gas abundance measurements (e.g., K-Ar geochronology, (U-Th)/He geochronology, noble gas cosmogenic chronology). Modeling indicates this effect in a system with a 10 L reservoir reaches a bias of 1% before 1000 pipette aliquants have been removed from the system, and a bias of 10% before 10,000 aliquants. Herein we explore the causes and effects of this problem, which is the result of volume changes during valve closure. We also present a solution in the form of an electropneumatic pressure regulator that can precisely control valve motion. This solution reduces the effect to ∼0.3% even after 10,000 aliquants have been removed from a 10 L reservoir.