Publications

Abstract Support for coastal wetland restoration projects that consider carbon (C) storage as a climate mitigation benefit is growing as coastal wetlands are sites of substantial C sequestration. However, the climate footprint of wetland restoration remains controversial as wetlands can also be large sources of methane (CH 4 ). We quantify the vertical fluxes of C in restored fresh and oligohaline nontidal wetlands with managed hydrology and a tidal euhaline marsh in California's San Francisco Bay‐Delta. We combine the use of eddy covariance atmospheric flux measurements with 210 Pb‐derived soil C accumulation rates to quantify the C sequestration efficiency of restored wetlands and their associated climate mitigation service. Nontidal managed wetlands were the most efficient in burying C on‐site, with soil C accumulation rates as high as their net atmospheric C uptake (−280 ± 90 and −350 ± 150 g C m −2 yr −1 ). In contrast, the restored tidal wetland exhibited lower C burial rates over decadal timescales (70 ± 19 g C m −2 yr −1 ) that accounted for ∼13%–23% of its annual C uptake, suggesting that the remaining fraction is exported via lateral hydrologic flux. From an ecosystem radiative balance perspective, the restored tidal wetland showed a > 10 times higher CO 2 ‐sequestration to CH 4 ‐emission ratio than the nontidal managed wetlands. Thus overall, tidal wetland restoration resulted in a negative radiative forcing (cooling) through increased soil C accumulation, while nontidal wetland restoration led to an early positive forcing (warming) through increased CH 4 emissions potentially lasting between 2.1 ± 2.0 to 8 ± 4 decades.

An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We investigate earth abundant materials for thin-film solar cells that can meet tens of terawatts level deployment potential. Candidate materials are identified by combinatorial search, large-scale electronic structure calculations, and literature reviews. We identified cuprous oxide (Cu2O) as a prototype candidate for investigation as an absorber layer in thin film solar cells. Cu2O thin films are deposited by reactive DC magnetron sputtering and characterized. In order to tailor electrical properties, we modify grain structure, and add defects that enhance electron transport, maintaining desired optical gap.

Abstract The surface expression of CD3-associated TCR chains on hybridoma cell lines derived from adult gamma delta thymocytes was analyzed. These cell lines were unusual, in that a) they expressed a surface heterodimer consisting of a 40- and a 42-kDa chain, i.e., comprised of chains different from any previously reported gamma delta-TCR all of which express C gamma 1- or C gamma 2-encoded gamma-chains; b) their CD3-associated TCR could not be categorized as alpha beta-TCR dimers, despite the similarities in m.w. of the TCR chains, because full size 1.3-kb beta-chain mRNA capable of encoding a functional beta-chain could not be detected in these cells; c) neither of the receptor chains could be precipitated with anti-C gamma 1C gamma 2-peptide antisera. Biochemical analysis demonstrated that the 42-kDa delta-chain is a novel chain, which differs from any reported delta-chains in size, charge and number of glycosylation sites. Collectively, the data on analysis of the 40-kDa chain strongly suggest that it represents a gamma-chain encoded for by the C gamma 4 locus, protein products of which have not yet been reported in the thymus. This gamma-chain was also unique, in that its isoelectric point was much lower than that of other gamma-chains. The gamma- and delta-chains on these C gamma 4-expressing hybridomas were indistinguishable from one another in size and charge (as determined by nonequivalent pH gradient electrophoresis/SDS-PAGE analysis and analysis after endoglycosidase treatment). Because the cell lines were randomly chosen from large panels of hybridomas, these results may well imply strikingly nonrandom pairing of thymocyte-derived C gamma 4 chains and the delta-chains reported here. Thus, only limited additional gamma delta repertoire diversity may be generated by availability of this gamma delta-TCR in the thymus.

Metastable carbonates play important roles in geochemistry, biomineralization and serve as model systems for nonclassical theories of nucleation and growth. Balcite (Ca<sub>0.5</sub>Ba<sub>0.5</sub>CO<sub>3</sub>) is a remarkable carbonate phase that is isostructural with a high-temperature modification of calcite (CaCO<sub>3</sub>), yet can be synthesized at ambient conditions. Here, we investigate crystallization pathways in the Ba-Ca-CO<sub>3</sub>-H<sub>2</sub>O system, with a focus on the transformation of amorphous calcium barium carbonate (ACBC) to balcite and subsequent decomposition into the equilibrium calcite (CaCO3) and witherite (BaCO<sub>3</sub>) phases. Density functional theory calculations show that balcite is an unstable solid solution (Ca<sub>1-x</sub>BaxCO<sub>3</sub>, R<sub>3¯</sub> m) in the range 0.17 < x < 0.5, but is accessible through the amorphous ACBC precursor for x ≲ 0.5, and predict its decomposition into calcite and witherite. We confirm this pathway experimentally but found demixing to proceed slowly and remain incomplete even after 9 months. Nucleation kinetics of balcite from ACBC was assessed using a microfluidic assay, where increasing barium content led to a surprising increase in the balcite nucleation rate, despite decreasing thermodynamic driving force. We attribute crystallization rates that dramatically accelerate with time to changes in interfacial structure and composition during coarsening of the amorphous precipitate. By carefully quantifying the thermodynamic and kinetic contributions in the multistep crystallization of a metastable carbonate, we produce insights that allow us to better interpret the formation and persistence of metastable minerals in natural and synthetic environments.

The Li₂S-P₂S₅ pseudo-binary system has been a valuable source of promising superionic conductors, with α-Li₃PS₄, β-Li₃PS₄, HT-Li₇PS₆, and Li₇P₃S₁₁ having excellent room-temperature Li-ion conductivity >0.1 mS/cm. The metastability of these phases at ambient temperature motivates a study to quantify their thermodynamic accessibility. Through calculating the electronic, configurational, and vibrational sources of free energy from first principles, a phase diagram of the crystalline Li₂S-P₂S₅ space is constructed. New ground-state orderings are proposed for α-Li₃PS₄, HT-Li₇PS₆, LT-Li₇PS₆, and Li₇P₃S₁₁. Well-established phase stability trends from experiments are recovered, such as polymorphic phase transitions in Li₇PS₆ and Li₃PS₄, and the instability of Li₇P₃S₁₁ at high temperature. At ambient temperature, it is predicted that all superionic conductors in this space are indeed metastable but thermodynamically accessible. Vibrational and configurational sources of entropy are shown to be essential toward describing the stability of superionic conductors. New details of the Li sublattices are revealed and are found to be crucial toward accurately predicting configurational entropy. All superionic conductors contain significant configurational entropy, which suggests an inherent correlation between fast Li diffusion and thermodynamic stability arising from the configurational disorder.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.