Focusing on the idea that multivalent cations affect SOM matrix and surface, we treated peat and soil samples by solutions of NaCl, CaCl2 or AlCl3. 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.
The coupled transport of pollutants that are adsorbed to colloidal particles has always been a major topic for environmental sciences due to many unfavorable effects on soils and groundwater. This laboratory column study was conducted under saturated moisture conditions to compare the hydrophobic character of the suspended and mobilized colloids in the percolates released from a wettable subsoil and a water repellent topsoil. Both soils with different organic matter content were analyzed for wettability changes before and after leaching using sessile drop contact angles as well as water and ethanol sorptivity curves, summarized as repellency index. Hydrophobicity of the effluent suspensions was assessed using the C18 adsorption method. Water repellency level of the repellent soil decreased after leaching but remained on a lower level of water repellency, while, the wettable soil remained wettable. The leached colloids from the repellent soil were predominantly hydrophilic and the percentage of the hydrophobic colloid fraction in the effluent did not systematically changed with time. Total colloid release depended on soil carbon stock but not on soil wettability. Our results suggest that due to the respective character of transported colloids a similar co-transport mechanism for pollutants
may occur which does not depend explicitly on soil wettability of the releasing horizon, but could be more affected by total SOM content. Further studies with a wider range of soils are necessary to determine if the dominant hydrophilic character of leached colloids is typical. Due to the mostly hydrophilic colloid character we conclude also that changes in wettability status, i.e. of wettable subsoil horizons due to the leachate, may not necessarily occur very fast, even when the overlaying topsoil is a repellent soil horizon with a high organic matter content.
Most recent studies on soil water repellency (WR) were limited to the humous topsoil or to shallow subsoil layers slightly below the main root zone to approximately 0.5 m depth. Hence, the main objective of the present study was to investigate the wettability pattern of a forest soil including the deeper subsoil. The selected site was a 100 years old beech forest on a well-drained sandy Cambisol in northern Germany which showed moderate to partly extended acidification. Results obtained from three sampling transects (3 m length, 2 m depth; sampling grid 8 × 8 samples per transect; minimum distance of sampling locations to nearest tree about 0.5 m) show that contact angles (CA) were always in the subcritical WR range (0° < CA < 90°). Significant impact of the tree distance on WR was not observed for any of the transects. A prominent feature of two transects was the minimum WR level (CA < 10°) for samples with soil organic carbon (SOC) contents around 0.25-0.4%. For the topsoils it was observed that CA increased with SOC content from that minimum to a maximum CA of 60-75° for transects 1 and 2 with mean pH values < 3.5. For transect 3 with slightly higher average pH close to 4.0, average CA of samples were always < 10° and showed no trend to increase with increasing SOC content or other soil parameters like N content or C/N ratio. Subsoil samples, however, behave differently with respect to SOC: for these samples, generally low in SOC, the CA increase with decreasing SOC occurred at all transects for approximately 50% of the samples but did not show any clear tendencies with respect to further parameters like texture, pH or N content. We conclude that the SOC content is the most prominent parameter determining wettability, either positively correlated with WR for topsoils or negatively correlated for subsoil samples very low in SOC. We finally conclude for moderately acid beech forest stands that emerging WR starts in the A horizon after reaching a pH lower than 3.5, whereas subsoil WR might appear already at higher pH values. Even SOC contents of ∼0.01-0.02% turned out to be very effective in increasing the CA up to 70°, which points out clearly the importance of small amounts of soil organic matter in affecting subsoil wettability. With respect to site hydrology we conclude that ongoing acidification as well as predicted higher frequencies of extended droughts due to climate change will promote the occurrence of WR with corresponding implications for site and catchment hydrology.