Langmuir : the ACS journal of surfaces and colloids, 09 October 2018, Vol.34(40), pp.12174-12182
Adsorption is the main mechanism of capturing water in soil organic matter (SOM) under arid conditions. This process is governed by hydrophilic sites, which are gradually bridged via water molecule bridges (WaMB). Until now, the link between WaMB and other types of water molecules occurring in SOM during sorption has not been systematically investigated. In this work, we compared the formation and stability of WaMB simultaneously with the total water content, strength of water binding, and kinetics of water sorption in a vacuum-dried model SOM (sapric histosol) exposed to different relative water pressures. The same parameters were then determined in SOM exposed to reduced relative pressures. The adsorption resulted in an adsorption isotherm with a Langmuir-like part below a relative pressure of 0.5 and a Brunauer-Emmett-Teller-like isotherm at higher relative pressures. The WaMB formation was observed at a relative pressure of 0.32, which represented the pressure at which Langmuir-like part reached a plateau. The binding energy showed a linear decrease with an increasing pressure; the slope increased at a relative pressure of 0.46. Reduction of relative pressures above 0.46 showed that the water content remained constant, but the binding energy was lowered. In contrast, below a relative pressure of 0.46, the water content decreased, but the binding energy was not changed. The results indicate that in SOM exposed to different relative pressures, water exists in three types: first, it is strongly bound to primary sorption sites (Langmuir-like), second, it occurs in the form of WaMB water, which bridges functional groups and where predominates water-water interactions, and third, it occurs in the form of phase water, which is located in larger pores similar to the pure water phase. The latter either surrounds the WaMB and destabilizes it or, for higher water content, links individual WaMB and successively reduces their stabilizing effect. Formation of phase water leads to swelling processes including plasticizing effects and potential volume changes of SOM. Accordingly, the results suggest that at lower water relative pressures WaMB stabilizes the SOM structure, whereas at higher water relative pressures, it influences the formation of phase water and thereby the total water content in SOM.
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