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A new analytical method is proposed for measuring the deuterium to hydrogen ratio (D/H) of non-stoichiometric water in hydrous minerals via pyrolysis facilitated gas-chromatography - isotope ratio mass spectrometry (GC-IRMS). Previously published analytical methods have reported a poorly understood nonlinear dependence of D/H on sample size, for which any

A new analytical method is proposed for measuring the deuterium to hydrogen ratio (D/H) of non-stoichiometric water in hydrous minerals via pyrolysis facilitated gas-chromatography - isotope ratio mass spectrometry (GC-IRMS). Previously published analytical methods have reported a poorly understood nonlinear dependence of D/H on sample size, for which any accurate correction is difficult. This sample size effect been variously attributed to kinetic isotope fractionation within the mass spectrometer and peripheral instruments, ion source linearity issues, and an unstable H_3^+-factor or incorrect H_3^+-factor calculations. The cause of the sample size effect is here identified by examinations of individual chromatograms as well as bulk data from chromatographic peaks. It is here determined that it is primarily an artifact of the calculations employed by the manufacturer's computer program, used to both monitor the functions of the mass spectrometer and to collect data. Ancillary causes of the sample size effect include a combination of persistent background interferences and chromatographic separation of the isotopologues of molecular hydrogen. Previously published methods are evaluated in light of these findings. A new method of H_3^+-factor and D/H calculation is proposed which makes portions of the Isodat software as well as other published calculation methods unnecessary. Using this new method, D/H is measured in non-stoichiometric water in chert from the Cretaceous Edwards Group, Texas, as well as the Precambrian Kromberg Formation, South Africa, to assess hydrological conditions as well as to estimate the maximum average surface temperature during precipitation of the chert. Data from Cretaceous chert are consistent with previously published data and interpretations, based upon conventional analyses of large samples. Data from Precambrian chert are consistent with maximum average surface temperatures approaching 65°C during the Archean, instead of the much lower temperatures derived from erroneous methods of sample preparation and analysis. D/H is likewise measured in non-stoichiometric water in silicified basalt from the Precambrian Hooggenoeg Complex, South Africa. Data are shown to be consistent with D/H of the Archean ocean similar to present day values.
ContributorsSheehan, Michael Robert (Author) / Knauth, Leroy P (Thesis advisor) / Anbar, Ariel (Committee member) / Farmer, Jack (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into

Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into these minerals.

Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.

These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
ContributorsChen, Xinming (Author) / Anbar, Ariel (Thesis advisor) / Herckes, Pierre (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Education through field exploration is fundamental in geoscience. But not all students enjoy equal access to field-based learning because of time, cost, distance, ability, and safety constraints. At the same time, technological advances afford ever more immersive, rich, and student-centered virtual field experiences. Virtual field trips may be the only

Education through field exploration is fundamental in geoscience. But not all students enjoy equal access to field-based learning because of time, cost, distance, ability, and safety constraints. At the same time, technological advances afford ever more immersive, rich, and student-centered virtual field experiences. Virtual field trips may be the only practical options for most students to explore pedagogically rich but inaccessible places. A mixed-methods research project was conducted on an introductory and an advanced geology class to explore the implications of learning outcomes of in-person and virtual field-based instruction at Grand Canyon National Park. The study incorporated the Great Unconformity in the Grand Canyon, a 1.2 billion year break in the rock record; the Trail of Time, an interpretive walking timeline; and two immersive, interactive virtual field trips (iVFTs). The in-person field trip (ipFT) groups collectively explored the canyon and took an instructor-guided inquiry hike along the interpretive Trail of Time from rim level, while iVFT students individually explored the canyon and took a guided-inquiry virtual tour of Grand Canyon geology from river level. High-resolution 360° spherical images anchor the iVFTs and serve as a framework for programmed overlays that enable interactivity and allow the iVFT to provide feedback in response to student actions. Students in both modalities received pre- and post-trip Positive and Negative Affect Schedules (PANAS). The iVFT students recorded pre- to post-trip increases in positive affect (PA) scores and decreases in negative (NA) affect scores, representing an affective state conducive to learning. Pre- to post-trip mean scores on concept sketches used to assess visualization and geological knowledge increased for both classes and modalities. However, the iVFT pre- to post-trip increases were three times greater (statistically significant) than the ipFT gains. Both iVFT and ipFT students scored 92-98% on guided-inquiry worksheets completed during the trips, signifying both met learning outcomes. Virtual field trips do not trump traditional in-person field work, but they can meet and/or exceed similar learning objectives and may replace an inaccessible or impractical in-person field trip.
ContributorsRuberto, Thomas (Author) / Semken, Steve (Thesis advisor) / Anbar, Ariel (Committee member) / Brownell, Sara (Committee member) / Arizona State University (Publisher)
Created2018