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Detrital zircon (DZ) U–Pb geochronology has improved the way geologists approach questions of sediment provenance and stratigraphic age. However, there is debate about what constitutes an appropriate sample size (i.e., the number of dates in a DZ sample,n), which depends on project objectives, sample complexity, and, critically, analytical budget. Additionally, there is ongoing concern about bias introduced by zircon grain size. We tested a recently developed rapid (3 s/analysis) data acquisition method by multicollector laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) that incorporates an automated selection routine and calculates two‐dimensional grain geometry from polished sample surfaces. Eleven samples were analysed from below and above the Late Cretaceous (Campanian) basal Castlegate unconformity of the Book Cliffs, Utah, in a down‐depositional‐dip transect including Price, Horse, Tusher, and Thompson canyons. 12,448 new concordant dates were generated during two measurement sessions. Results are consistent with recent studies suggesting there is no major provenance change and little time (1–2 Myr) represented across the unconformity. Grain size and sample size both exert a strong control on sample dissimilarity. Age distributions constructed from subsamples of large grains are systematically less similar to whole samples; age distributions composed of small grains are overall more similar to whole samples. As such, North American sediment sources that produce large grains such as the Grenville and Yavapi‐Mazatzal belts can bias age distributions if only large grains are analysed. A sample size ofn = 100 is inadequate for characterizing age distributions as complex as those of the Book Cliffs, whereas a sample size ofn = 300 provides good characterization. Sample size ofn ≈ 1000 or more is unnecessary unless project objectives include scanning for subordinate age groups, such as when identifying the youngest grains for calculating a maximum depositional age (MDA). Dates used in MDA calculations acquired with rapid acquisition are best re‐analysed with longer LA‐ICP‐MS acquisition methods or isotope dilution thermal ionization mass spectrometry for increased accuracy and precision. We include new MATLAB code and open‐source software programs,DZpickandDZmda, for automated spot picking and calculating MDAs.

 

Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 

Titanite U–Pb geochronology is a promising tool to date high-temperature tectonic processes, but the extent to and mechanisms by which recrystallization resets titanite U–Pb dates are poorly understood. This study combines titanite U–Pb dates, trace elements, zoning, and microstructures to directly date deformation and fluid-driven recrystallization along the Coast shear zone (BC, Canada). Twenty titanite grains from a deformed calc-silicate gneiss yield U–Pb dates that range from ~ 75 to 50 Ma. Dates between ~ 75 and 60 Ma represent metamorphic crystallization or inherited detrital cores, whereas ~ 60 and 50 Ma dates reflect localized, grain-scale processes that variably recrystallized the titanite. All the analyzed titanite grains show evidence of fluid-mediated dissolution–reprecipitation, particularly at grain rims, but lack evidence of thermally mediated volume diffusion at a metamorphic temperature of > 700 °C. The younger U–Pb dates are predominantly found in bent portions of grains or fluid-recrystallized rims. These features likely formed during ductile slip and associated fluid flow along the Coast shear zone, although it is unclear whether the dates represent 10 Myr of continuous recrystallization or incomplete resetting of the titanite U–Pb system during a punctuated metamorphic event. Correlations between dates and trace-element concentrations vary, indicating that the effects of dissolution–reprecipitation decoupled U–Pb dates from trace-element concentrations in some grains. These results demonstrate that U–Pb dates from bent titanite lattices and titanite subgrains may directly date crystal-plastic deformation, suggesting that deformation microstructures enhance fluid-mediated recrystallization, and emphasize the complexity of fluid and deformation processes within and among individual grains.