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A conceptual model of organo-mineral interactions in soils: self-assembly of organic molecular fragments into zonal structures on mineral surfaces

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Abstract

In this paper, we propose a structure for organo-mineral associations in soils based on recent insights concerning the molecular structure of soil organic matter (SOM), and on extensive published evidence from empirical studies of organo-mineral interfaces. Our conceptual model assumes that SOM consists of a heterogeneous mixture of compounds that display a range of amphiphilic or surfactant-like properties, and are capable of self-organization in aqueous solution. An extension of this self-organizational behavior in solution, we suggest that SOM sorbs to mineral surfaces in a discrete zonal sequence. In the contact zone, the formation of particularly strong organo-mineral associations appears to be favored by situations where either (i) polar organic functional groups of amphiphiles interact via ligand exchange with singly coordinated mineral hydroxyls, forming stable inner-sphere complexes, or (ii) proteinaceous materials unfold upon adsorption, thus increasing adhesive strength by adding hydrophobic interactions to electrostatic binding. Entropic considerations dictate that exposed hydrophobic portions of amphiphilic molecules adsorbed directly to mineral surfaces be shielded from the polar aqueous phase through association with hydrophobic moieties of other amphiphilic molecules. This process can create a membrane-like bilayer containing a hydrophobic zone, whose components may exchange more easily with the surrounding soil solution than those in the contact zone, but which are still retained with considerable force. Sorbed to the hydrophilic exterior of hemimicellar coatings, or to adsorbed proteins, are organic molecules forming an outer region, or kinetic zone, that is loosely retained by cation bridging, hydrogen bonding, and other interactions. Organic material in the kinetic zone may experience high exchange rates with the surrounding soil solution, leading to short residence times for individual molecular fragments. The thickness of this outer region would depend more on input than on the availability of binding sites, and would largely be controlled by exchange kinetics. Movement of organics into and out of this outer region can thus be viewed as similar to a phase-partitioning process. The zonal concept of organo-mineral interactions presented here offers a new basis for understanding and predicting the retention of organic compounds, including contaminants, in soils and sediments.

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Acknowledgements

We thank M.S. Torn, T. Filley, C. Swanston, M. Kramer, G. Sposito and especially B. Caldwell for discussions and helpful comments on earlier drafts of the manuscript. The comments of J. Chorover were particularly valuable and are gratefully appreciated. The contribution of MK results from previous support through the German Science Foundation (DFG) priority program SPP 1090 and from current financial support by the Climate Change Research Division, Office of Science, U.S. Department of Energy under Contract No. DE-AC03-76SF00098. Partial funding was provided by NSF SGER and USDA CSRI grants to PS and MK and by the Andrews LTER program.

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  1. Earth Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA

    M. Kleber

  2. Department of Forest Science, Oregon State University, Corvallis, OR, 97331, USA

    P. Sollins

  3. Department of Environmental Science, Policy and Management, University of California, #3114 Mulford Hall, Berkeley, CA, 94720-3114, USA

    R. Sutton

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Kleber, M., Sollins, P. & Sutton, R. A conceptual model of organo-mineral interactions in soils: self-assembly of organic molecular fragments into zonal structures on mineral surfaces. Biogeochemistry 85, 9–24 (2007). https://doi.org/10.1007/s10533-007-9103-5

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