Interactions between cations and water molecule bridges in soil organic matter

Abstract

Nutrient release, soil wettability, water binding, and matrix rigidity of soil organic matter (SOM) can be affected by cross-links between segments of SOM, cations, and water molecule bridges (WaMB). Not all cation effects on SOM can be explained with the currently accepted idea that multivalent cations cross-link organic matter segments via direct cation bridges (CaB). The objective was to understand these interactions and their effect on SOM matrix rigidity and wettability. We modified cation composition of two peats and an organic surface layer (OSL) using cation exchange resin to remove cations and solutions of Na+, Ca2+, or Al3+ to enrich samples with cations. SOM matrix rigidity was determined at 4 and >8 weeks after treatment via the WaMB transition temperature T*, using differential scanning calorimetry. Wettability was measured via sessile drop contact angle (CA). The effect of cation removal on T* depended on cation exchange capacity and initial cation content. Cation addition to OSL increased T*. This effect increased with increasing cation loading and valency, and T* correlated with CA. Classical cross-linking can neither explain the higher heterogeneous matrix of Ca-treated than Al-treated samples nor the aging-induced convergence of T* for different cations and concentrations. The latter is likely due to interaction between CaB and WaMB in SOM. Associations of CaB and WaMB evolve slowly and form a supramolecular network in SOM. Those dynamic associations can fix molecular arrangements inducing water repellency and increase kinetic barriers for the release and uptake of water and nutrients from aged soil.