Protein–Mineral Interactions: Molecular Dynamics Simulations Capture Importance of Variations in Mineral Surface Composition and Structure

Molecular dynamics simulations, conventional and metadynamics, were performed to determine the interaction of model protein Gb1 over kaolinite (001), Na⁺-montmorillonite (001), Ca²⁺-montmorillonite (001), goethite (100), and Na⁺-birnessite (001) mineral surfaces. Gb1, a small (56 residue) protein with a well-characterized solution-state nuclear magnetic resonance (NMR) structure and having α-helix, 4-fold β-sheet, and hydrophobic core features, is used as a model protein to study protein soil mineral interactions and gain insights on structural changes and potential degradation of protein. From our simulations, we observe little change to the hydrated Gb1 structure over the kaolinite, montmorillonite, and goethite surfaces relative to its solvated structure without these mineral surfaces present. Over the Na⁺ -birnessite basal surface, however, the Gb1 structure is highly disturbed as a result of interaction with this birnessite surface. Unraveling of the Gb1 β-sheet at specific turns and a partial unraveling of the α-helix is observed over birnessite, which suggests specific vulnerable residue sites for oxidation or hydrolysis possibly leading to fragmentation

Elemental Composition of Natural Nanoparticles and Fine Colloids in European Forest Stream Waters and Their Role as Phosphorus Carriers

"This is the peer reviewed version of the following article: Gottselig, N., W. Amelung, J. W. Kirchner, R. Bol, W. Eugster, S. J. Granger, C. Hernández-Crespo, et al. 2017. Elemental Composition of Natural Nanoparticles and Fine Colloids in European Forest Stream Waters and Their Role as Phosphorus Carriers. Global Biogeochemical Cycles 31 (10). American Geophysical Union (AGU): 1592 1607. doi:10.1002/2017gb005657, which has been published in final form at https://doi.org/10.1002/2017GB005657. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] Biogeochemical cycling of elements largely occurs in dissolved state, but many elements may also be bound to natural nanoparticles (NNP, 1-100 nm) and fine colloids (100-450 nm). We examined the hypothesis that the size and composition of stream water NNP and colloids vary systematically across Europe. To test this hypothesis, 96 stream water samples were simultaneously collected in 26 forested headwater catchments along two transects across Europe. Three size fractions (similar to 1-20 nm, >20-60 nm, and >60 nm) of NNP and fine colloids were identified with Field Flow Fractionation coupled to inductively coupled plasma mass spectrometry and an organic carbon detector. The results showed that NNP and fine colloids constituted between 2 +/- 5% (Si) and 53 +/- 21% (Fe; mean +/- SD) of total element concentrations, indicating a substantial contribution of particles to element transport in these European streams, especially for P and Fe. The particulate contents of Fe, Al, and organic C were correlated to their total element concentrations, but those of particulate Si, Mn, P, and Ca were not. The fine colloidal fractions >60 nm were dominated by clay minerals across all sites. The resulting element patterns of NNP <60 nm changed from North to South Europe from Fe-to Ca-dominated particles, along with associated changes in acidity, forest type, and dominant lithology.The authors gratefully acknowledge the assistance of the following people in locating suitable sampling sites, contacting site operators, performing the sampling, and providing data: A. Avila Castells (Autonomous University of Barcelona), R. Batalla (University of Lleida), P. Blomkvist (Swedish University of Agricultural Sciences), H. Bogena (Julich Research Center), A.K. Boulet (University of Aveiro), D. Estany (University of Lleida), F. Garnier (French National Institute of Agricultural Research), H.J. Hendricks-Franssen (Research Center Julich), L. JacksonBlake (James Hutton Institute, NIVA), T. Laurila (Finnish Meteorological Institute), A. Lindroth (Lund University), M.M. Monerris (Universitat Politecnica de Valencia), M. Ottosson Lofvenius (Swedish University of Agricultural Sciences), I. Taberman (Swedish University of Agricultural Sciences), F. Wendland (Research Center Julich), T. Zetterberg (Swedish University of Agricultural Sciences and The Swedish Environmental Research Institute, IVL) and further unnamed contributors. The Swedish Infrastructure for Ecosystem Science (SITES) and the Swedish Integrated Monitoring, the latter financed by the Swedish Environmental Protection Agency, and ICOS Sweden have supported sampling and provided data for the Swedish sites. J.J.K. gratefully acknowledges the support from CESAM (UID/AMB/50017/2013), funded by the FCT/MCTES (PIDDAC) with cofunding by FEDER through COMPETE. N.G. gratefully acknowledges all those who contributed to organizing and implementing the continental sampling. The raw data can be found at http://hdl.handle.net/2128/14937. This project was partly funded by the German Research Foundation (DFG KL2495/1-1).Gottselig, N.; Amelung, W.; Kirchner, J.; Bol, R.; Eugster, W.; Granger, S.; Hernández Crespo, C.... 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420,000 year assessment of fault leakage rates shows geological carbon storage is secure

Carbon capture and storage (CCS) technology is routinely cited as a cost effective tool for climate change mitigation. CCS can directly reduce industrial CO2 emissions and is essential for the retention of CO2 extracted from the atmosphere. To be effective as a climate change mitigation tool, CO2 must be securely retained for 10,000 years (10 ka) with a leakage rate of below 0.01% per year of the total amount of CO2 injected. Migration of CO2 back to the atmosphere via leakage through geological faults is a potential high impact risk to CO2 storage integrity. Here, we calculate for the first time natural leakage rates from a 420 ka paleo-record of CO2 leakage above a naturally occurring, faulted, CO2 reservoir in Arizona, USA. Surface travertine (CaCO3) deposits provide evidence of vertical CO2 leakage linked to known faults. U-Th dating of travertine deposits shows leakage varies along a single fault and that individual seeps have lifespans of up to 200 ka. Whilst the total volumes of CO2 required to form the travertine deposits are high, time-averaged leakage equates to a linear rate of less than 0.01%/yr. Hence, even this natural geological storage site, which would be deemed to be of too high risk to be selected for engineered geologic storage, is adequate to store CO2 for climate mitigation purposes

Non-enzymatic U(VI) Interactions with Biogenic Mackinawite

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium

Protein-Mineral Interactions: Molecular Dynamics Simulations Capture Importance of Variations in Mineral Surface Composition and Structure.

Molecular dynamics simulations, conventional and metadynamics, were performed to determine the interaction of model protein Gb1 over kaolinite (001), Na(+)-montmorillonite (001), Ca(2+)-montmorillonite (001), goethite (100), and Na(+)-birnessite (001) mineral surfaces. Gb1, a small (56 residue) protein with a well-characterized solution-state nuclear magnetic resonance (NMR) structure and having α-helix, 4-fold β-sheet, and hydrophobic core features, is used as a model protein to study protein soil mineral interactions and gain insights on structural changes and potential degradation of protein. From our simulations, we observe little change to the hydrated Gb1 structure over the kaolinite, montmorillonite, and goethite surfaces relative to its solvated structure without these mineral surfaces present. Over the Na(+)-birnessite basal surface, however, the Gb1 structure is highly disturbed as a result of interaction with this birnessite surface. Unraveling of the Gb1 β-sheet at specific turns and a partial unraveling of the α-helix is observed over birnessite, which suggests specific vulnerable residue sites for oxidation or hydrolysis possibly leading to fragmentation