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Isotopes, Interfaces, and Geochemical Transformations August 7-8, 2017 Geosciences Research Program, Office of Basic Energy Sciences

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Isotopes, Interfaces, and Geochemical Transformations August 7-8, 2017 Geosciences Research Program, Office of Basic Energy Sciences Isotopes, Interfaces, and Geochemical Transformations August 7-8, 2017 Geosciences Research Program, Office of Basic Energy Sciences Shining New Light on the Structure and Crystallization of Amorphous (Basic) Calcium Carbonate Novel synthesis: Scientific Achievement Rate of mixing is the key For the first time, the locations and hydrogen- bonded network in amorphous (basic) calcium carbonate, A(B)CC, have been measured directly using neutron diffraction on deuterated reactants and the key role that water and hydroxide play in stabilizing and controlling the A(B)CC structure has been revealed. Significance and Impact A(B)CC to calcite & portlandite crystallization This work provides insights into controlling the synthesis, crystallization and polymorphous state of A(B)CC and the roles of water and dissolved species. Research Details − Novel synthesis based on kinetically controlled Bound D2O/OD species are captured by Neutron PDF processes and fast centrifugal mixing of solutions − In situ neutron diffraction used to follow the crystallization pathway Wang, H.-W.; Daemen, L.L.; Cheshire, C.C.; Kidder, M.K.; Stack, A.G.; Allard, L.F.; − Neutron Pair Distribution Functions (PDF) showed Neuefeind, J.; Olds, D.; Liu, J; Page, K. Synthesis and Structure of Synthetically Pure and superior sensitivity to pairs involving deuterium and Deuterated Amorphous (Basic) Calcium Carbonates. Chem. Comm. 2017, 53, 2492-2495. carbon FOREWORD “Isotopes, Interfaces, and Geochemical Transformations” is the 22nd in a series of Geosciences Research Program Symposia dating from 1995. These symposia are topically focused meetings for principal investigators in the program and provide opportunities for our investigators to give presentations on their BES-supported research. It is hoped that this meeting will provide an environment conducive to building collaborations and identifying opportunities for new research directions. In addition to seven topical sessions, this year’s program has a poster session and an invited evening talk to be given by Prof. Woody Fischer of Caltech. I would like to thank this year’s Session Chairs: Bill Casey (UC Davis), Ian Bourg (Princeton), Sue Brantley (Penn State), Dave Dixon (Alabama), Paul Fenter (Argonne), Mike Hochella (Virginia Tech/PNNL), and Arndt Schimmelmann (Indiana). I would also like to thank Diane Marceau of the Chemical Sciences, Geosciences, and Biosciences (CSGB) Division and Connie Lansdon of the Oak Ridge Institute for Science and Educations (ORISE) for their excellent contributions in organizing the technical and logistical aspects of this meeting. Finally, I thank all the scientists whose vision and creativity in research and dedication and thoughtfulness in peer review have shaped the ongoing research mission of the Office of Basic Energy Sciences Geosciences Program. Looking forward to an outstanding series of presentations. Jim Rustad Geosciences Research Program Office of Basic Energy Sciences US Department of Energy Cover Images Top left: Molecular-level simulation of aggregated gibbsite particles, Greathouse et al. Sandia National Laboratories. •– •– 3- Top right: Photo-redox generation of C2O4 and CO2 in Fe(C2O4)3 Gilbert et al., Lawrence Berkeley National Lab and Pacific Northwest National Laboratory. Middle: Ion microprobe transect of 18O isotope variation in diagenetic carbonate cement. Valley et al., University of Wisconsin. Bottom left: Dynamics of rubidium sorption observed with time-resolved resonant anomalous x-ray reflectivity. Lee et al., Argonne National Laboratory. Bottom right: Neutron diffraction has been used to study the structure of amorphous calcium carbonate and its transformation to calcite, portlandite and lime. Stack et al. Oak Ridge National Laboratory. Agenda 2017 Geosciences Program PI Meeting U.S. Department of Energy Office of Basic Energy Sciences Chemical Sciences, Geosciences & Biosciences Division (CSGB) Sunday Aug 6 4:00-6:00 pm Registration (if you miss this, you may register in the morning) 8:00-11:00 pm Informal and optional no-host reception at the Black Olive Bar & Grill (in the National Conference Center facility) Monday Aug 7 7:00 am Breakfast 7:55 am Welcome, Jim Rustad, BES Geosciences Program Manager 8:00 am BES/CSGB Update and Outlook Bruce Garrett, CSGB Division Director Session 1 New Measurements in Isotope Geochemistry Bill Casey, Session Chair 8:30 am Isotopic structures of natural organic molecules John Eiler, Caltech 9:00 am Intra-molecular isotope study of light hydrocarbons Juske Horita, Texas Tech 9:30 am In situ microanalysis of O & C isotope ratios in carbonate cements: SIMS standardization and preliminary data from the Bakken formation John Valley, University of Wisconsin 10:00 am Break Session 2 Interfacial and Isotope Geochemistry Ian Bourg, Session Chair 10:30 am Controls on the isotopic composition and Mg/Ca of calcite Don DePaolo, Lawrence Berkeley National Laboratory 11:00 am Electrochemical kinetic isotope fractionation: theory and experiments Abby Kavner, UCLA 11:30 am Clumped isotope signatures in carbonate minerals Aradhna Tripati, UCLA 12:00 pm Lunch Monday Aug 7 (cont.) Session 3 Mineral and Surface Energetics Sue Brantley, Session Chair 1:30 pm Energetics of water, carbon dioxide, and ethanol adsorption on mineral surfaces Alex Navrotsky, UC Davis 2:00 pm Calorimetric insights into mineral-water interfaces: deciphering the anatomy of an enthalpy Nadine Kabengi, Georgia State 2:30 pm Ab initio thermodynamics of hydrated Mg and Ca carbonates Anne Chaka, Pacific Northwest National Laboratory 3:00 pm Break Session 4 3:30 pm Geosciences Program notes Jim Rustad, BES Geosciences Program Manager 4:00 pm Poster Session 6:00 pm Dinner 7:30 pm Invited Keynote Lecture Manganese and the development of photosynthesis Woody Fischer, Caltech Tuesday Aug 8 7:30 am Breakfast Session 5 Crystal Growth Dave Dixon, Session Chair 8:30 am Particle mediated growth of iron oxides Jim De Yoreo, Pacific Northwest National Laboratory 9:00 am Kinetics and thermodynamics of CaCO3 nucleation in an organic matrix Trish Dove, Virginia Tech 9:30 am Crystallization by particle attachment (CPA) in biominerals Pupa Gilbert, University of Wisconsin 10:00 Break Tuesday Aug 8 (cont.) Session 6 Mineral-Water Interfaces Paul Fenter, Session Chair 10:30 am Interfacial geochemistry of nanopores: Molecular behavior in subsurface environments Jeff Greathouse, Sandia National Laboratory 11:00 am Real-time observations of cation exchange at the muscovite (001) – water interface Sang Soo Lee, Argonne National Laboratory 2+ 11:30 am Comparison of H2O and Sr positions on barite {001} studied by atomic-scale simulation and X-ray scattering Jim Kubicki, University of Texas, El Paso 12:00 pm Lunch Session 7 Redox Processes Jim Rustad, Session Chair 1:30 pm Unraveling interfacial atom and electron exchange mechanisms in Fe(II)- catalyzed iron oxide recrystallization Kevin Rosso, Pacific Northwest National Laboratory 2:00 pm Kinetics of redox reactions of actinides on semiconducting minerals, as well as studtite and U60 clusters Udo Becker, University of Michigan 2:30 pm Iron redox and photo-redox reaction mechanism from time-resolved spectroscopy Ben Gilbert, Lawrence Berkeley National Laboratory 3:00 pm Break Session 8 Geochemical Transformations Arndt Schimmelmann, Session Chair 3:30 pm Diffusion and solubility of volatiles in cryptocrystalline materials and simple oxides: CO2 and N2 in chert and C isotopes in polycrystalline MgO Bruce Watson, Rensselaer Polytechnic Institute 4:00 pm Nanoscale stress-corrosion of silicate glass in aqueous solutions Louise Criscenti, Sandia National Laboratory 4:30 pm Insights into geochemical transformations probed by examining solution and solid phase structures using neutron diffraction and atomic-scale simulation Andrew Stack, Oak Ridge National Laboratory 5:00 pm Closing, Jim Rustad, DOE/OBES Posters Piotrek Zarzycki, Lawrence Berkeley National Laboratory Reactive molecular dynamics as a unique tool for understanding reactivity of mineral surfaces: Fe(II)-catalyzed recrystallization of goethite Paul Fenter, Argonne National Laboratory Imaging complex reactions at mineral-water interfaces Arndt Schimmelmann, Indiana University Genesis, storage, producibility, and natural leakage of shale gas Sue Brantley, Pennsylvania State University Investigating the roughness and advance rate of the weathering interface: shale, schist, diabase, granite, volcaniclastics, and serpentinite Dave Dixon, University of Alabama Computational studies of geochemical nanoparticles: A bottom-up approach Bill Casey, UC Davis An NMR probe for solution spectroscopy at geochemical pressures Mike Hochella, Virginia Tech New light shed on important Earth-relevant redox reactions observed at the nanoscale Ian Bourg, Princeton Stern layer structure and energetics at mica-water interfaces Vitaliy Starchenko, Oak Ridge National Laboratory Simulation of fracture dissolution in rocks: A 3D approach Anastasia Ilgen, Sandia (Jeff Greathouse/Louise Criscenti presenting) Adsorption of copper and iron on mesoporous alumina and silica Yuxin Wu, Lawrence Berkeley National Laboratory Geophysical methods for geochemical and hydrological process at mineral-water interfaces of geological media Isotopic structures of natural organic molecules John Eiler, Caltech We are in a period of remarkable innovation of the technologies, methods and fields of application of measurements of isotopic contents of natural and synthetic materials. Arguably the most complex and quickly changing part of
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