Interactions of organic compounds with soil components - elucidating mechanisms on a molecular level
Final Report Abstract
Within the scientific framework of the SPP 1315, “Biogeochemical interfaces in soil”, the major hypothesis of our project was that macroscopic physical and chemical features of BGIs originate from the microscopic (molecular level), and theoretical approaches can contribute to the understanding (exploring) them. To this end we contributed to unraveling of the complex architecture of BGIs by means of application and development of proper theoretical chemical techniques from fast force-field (FF) based up to quantum-chemical combining with molecular dynamics and/or Monte Carlo (multiscale modeling). As far as possible the outcomes of the modeling were compared with experimental results from our own project and other groups of the SPP. Batch sorption experiments were performed for a set of chemical species on selected soil minerals, charcoal, natural soils, and artificially produced soils. For aniline and 1-naphthylamine was shown that adsorption was stronger to the soil samples than to single soil constituents such as clay minerals emphasizing the role of organo-mineral associations. Quantum mechanical calculations revealed that formation of hydrogen bonds is the dominating binding mechanism in modeled complexes. Major results from theoretical investigations are the detailed characterization of surface properties of important soil minerals such as iron oxyhydroxides (e.g. goethite) and clays (e.g. kaolinite, montmorillonite). Reactive sites available for interactions with organic compounds, acid-base properties, swelling and hydration, wettability were described by applying molecular modeling methods. Multiradical features of black carbon were described by using model graphene flakes and advanced quantum chemical methods. Our theoretical investigations also provided numerous data on molecular interactions between polar and nonpolar organic chemicals (e.g. pesticide 4-chloro-2-methylphenoxyacetic acid (MCPA), polycyclic aromatic hydrocarbons, PAHs) and the inorganic and/or organic surfaces of soil constituents including soil organic matter nanopores. Within the project three concrete links between modeling and experiments were developed: (i) Force-field molecular dynamic approach was used in the study of hydrophobic/hydrophilic properties of organically coated silica surfaces that can represent BGIs of organo-mineral aggregates in soils. It was shown that wetting strongly depends on the type and density of coating. In parallel, experimental contact angle (CA) investigations were performed on the same model system by our cooperation partner. A good correspondence between measured and predicted CAs was obtained. (ii) The role of water molecular and cation bridges in the formation of supramolecular structures in soil organic matter (SOM) was investigated by theoretical methods and numerous structural model systems. The results supported the experimental findings of our cooperation partner, showing that moisture and aging are important factors affecting rigidity and stability of SOM. (iii) Interactions between the (110) goethite surface and MCPA were analyzed by theoretical methods. The two most stable structures were used to parameterize a surface complexation model (CD-MUSIC) using charge distributions and the adsorption constants. This procedure provided a good fit to the experimental data. It was shown how to directly and effectively link results from molecular modeling to the simulation of adsorption processes at continuum scale, one of the major objectives of the SPP 1315.
Publications
- Interaction of the 2.4-dichlorophenoxyacetic acid herbicide with soil organic matter moieties: a theoretical study. European Journal of Soil Science 58, 889-899, 2007
Aquino, A.J.A., Tunega, D., Haberhauer, G., Gerzabek, M.H. and H. Lischka
- Quantum chemical adsorption studies on the (110) surface of the mineral goethite. Journal of Physical Chemistry C 111, 877-885, 2007
Aquino, A.J.A. Tunega, D., Haberhauer, G., Gerzabek, M.H. and H. Lischka
- Acid-base properties of a goethite surface model: A theoretical view. Geochimica et Cosmochimica Acta 72, 3587-3602, 2008
Aquino, A.J.A., Tunega, D., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- Hydrogen bonds and solvent effects in soil processes: a theoretical view. In “Solvation Effects on Molecules and Biomolecules”, S. Canuto (ed.), pp. 321–347, 2008
Tunega, D., Aquino, A.J.A:, Gerzabek, M.H., Haberhauer, G., and H. Lischka
- The thermodynamic stability of hydrogen bonded and cation bridged complexes of humic acid models - A theoretical study. Chemical Physics 349, 69-76, 2008
Aquino, A.J.A., Tunega, D., Pasalic, H., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- Model study on sorption of polycyclic aromatic hydrocarbons to goethite. Journal of Colloid and Interface Science 330, 244-249, 2009
Tunega, D., Gerzabek, M. H., Haberhauer, G., Totsche, K. U., and H. Lischka
- Stabilizing Capacity of Water Bridges in Nanopore Segments of Humic Substances: A Theoretical Investigation. Journal of Physical Chemistry C 113, 16468-16475, 2009
Aquino, A. J. A., Tunega, D., Schaumann, G. E., Haberhauer, G., Gerzabek, M. H., and H. Lischka
- Biogeochemical interfaces in soil: The interdisciplinary challenge for soil science. Journal of Plant and Nutrition Soil Science 173, 88-99, 2010
Totsche, K.-U., Rennert, T., Gerzabek, M.H., Kögel-Knabner, I., Smalla, K., Spiteller, M., and H.-J.Vogel
- Adsorption of phenanthrene on Na-montmorillonite: A model study. Geoderma 169, 41-46, 2011
Meleshyn, A. and D. Tunega
- Molecular Dynamics Simulations of Water Molecule-Bridges in Polar Domains of Humic Acids. Environmental Science & Technology 45, 8411–8419, 2011
Aquino, A.J.A., Tunega, D., Pasalic, H., Schaumann, G.E., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- Sorption of selected aromatic substances - application of kinetic concepts and quantum mechanical modelling. Water, Air and Soil Pollution 215(1), 449-464, 2011
Klepsch, S., Aquino, A.J.A., Haas, U., Tunega, D., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- Study of solvent effect on the stability of water bridge-linked carboxyl groups in humic acid models. Geoderma 169, 20-26, 2011
Aquino, A.J.A., Tunega, D., Pasalic, H., Schaumann, G.E., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- The functionality of cation bridges for binding polar groups in soil aggregates. International Journal of Quantum Chemistry 111, 1531-1542, 2011
Aquino, A.J.A., Tunega, D., Schaumann, G., Haberhauer, G., Gerzabek, M.H., and H. Lischka
- Wettability of kaolinite (001) surfaces - Molecular dynamic study. Geoderma 169, 47-54, 2011
Solc, R., Gerzabek, M.H., Lischka, H., and D. Tunega
- Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging. Journal of Soils and Sediments 12(8), 1292-1298, 2012
Waldner, G., Friesl-Hanl, W., Haberhauer, G., Gerzabek, M.H.
- Proton transfer processes in polar regions of humic substances initiated by aqueous aluminum cation bridges: A computational study. Geoderma 213, 115-123, 2013
Aquino, A.J.A., Tunega, D., Schaumann, G.E., Haberhauer, G., Gerzabek, M.H., and H. Lischka
(See online at https://doi.org/10.1016/j.geoderma.2013.08.001) - Restructuring of a peat in interaction with multivalent cations: Effect of cation type and aging time. Plos One 8, e65359, 2013
Kunhi Mouvenchery, Y., Jaeger, A., Aquino, A.J.A., Tunega, D., Diehl, D., Bertmer, M., and G.E. Schaumann
(See online at https://doi.org/10.1371/journal.pone.0065359) - The multiradical character of one- and two-dimensional graphene nanoribbons. Angewandte Chemie - International Edition 52/9, 2581-2584, 2013. Deutsch: Angewandte Chemie 125, 2641-2644, 2013
Plasser, F., Pasalic, H., Gerzabek, M.H., Libisch, F., Reiter, R., Burgdörfer, J., Müller, T., Shepard, R., and H. Lischka
