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It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al3+, Ca2+ or Na+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

Focusing on the idea that multivalent cations affect SOM matrix and surface, we treated peat and soil samples by solutions of NaCl, CaCl 2 or AlCl 3 . Water binding was characterized with low field 1 H-NMR-relaxometry (20 MHz) and 1 H wideline NMR spectroscopy (400 MHz) and compared to contact angles. From 1 H wideline, we distinguished mobile water and water involved in water molecule bridges (WaMB). Large part of cation bridges (CaB) between SOM functional groups are associated with WaMB. Unexpectedly, 1 H NMRrelaxometry relaxation rates suggest that cross-linking in the Al-containing peat is not stronger than that by Ca.The relation between percentage of mobile water and WaMB water in the context of wettability and 1 H NMR relaxation times confirms that wettability controls the water film surrounding soil particles. Wettability is controlled by WaMB-CaB associations fixing hydrophilic functional groups in the SOM interior. This can lead to severe water repellency. Wettability decreases with increasing involvement of functional groups in CaB-WaMB associations. The results demonstrate the relevance of CaB and WaMB for the dynamics of biogeochemical and hydrological processes under field conditions, as only a few percent of organic matter can affect the physical, chemical, and biological functioning of the entire 3-phase ecosystem.