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 organo-mineral coatings of soil aggregates, cracks, and biopores control sorption and macropore-matrix exchange during preferential flow, in particular in the clay-illuvial Bt-horizon of Luvisols. The soil organic matter (SOM) composition has been hypothesized to explain temporal changes in the hydraulic properties of aggregate surfaces. The objective of this research was to find relations between the temporal change in wettability, in terms of droplet infiltration dynamics, and the SOM composition of coated and uncoated aggregate surfaces. We used 20 to 40 mm sized soil aggregates from the Bt2 horizon of a Haplic Luvisol from loess that were (i) coated, (ii) not coated (both intact), and (iii) aggregates from which coatings were removed (cut). The SOM composition of the aggregate surfaces was characterized by infrared spectroscopy in the diffuse reflection mode (DRIFT). A potential wettability index (PWI) was calculated from the ratio of hydrophobic and hydrophilic functional groups in SOM. The water drop penetration times (WDPT) and contact angles (CA) during droplet infiltration experiments were determined on dry and moist aggregate samples of the three types. The decrease in the CA with time was described using the power function (CA(t) = at–b). For dry aggregates, the WDPT values were larger for coated as compared to uncoated regions on the aggregate surfaces, and increased with increasing PWI value (R2 = 0.75). The a parameter was significantly related to the WDPT (R2 = 0.84) and to the PWI (R2 = 0.64). The relations between the b parameter and the WDPT (R2 = 0.61) and the PWI (R2 = 0.53) were also significant. The WDPT values of wet soil aggregates were higher than those of dry aggregates due to high water contents, which limited the droplet infiltration potential. At the wet aggregate surfaces, the WDPT values increased with the PWI of the SOM (R2 = 0.64). In contrast to dry samples, no significant relationships were found between parameters a or b of CA(t) and WDPT or PWI for wet aggregate surfaces. The results suggest that the effect of the SOM composition of coatings on surface wettability decreases with increasing soil moisture. In addition to the dominant impact of SOM, the wettability of aggregate surfaces could be affected by different mineralogical compositions of clay in coatings and interiors of aggregates. Particularly, wettability of coatings could be decreased by illite which was the dominant clay type in coatings. However, the influence of different clay mineral fractions on surface wettability was not due to small number of measurements (2 and 1 samples from coatings and interiors, respectively) quantified.
In agricultural land use, organic residues such as compost, digestate, and sewage sludge are discussed as costeffective soil conditioner that may improve the water holding capacity and crop available soil moisture. The objective of this study is to determine the effect of application of digestates with different compositions in maize, sugar beet and winter wheat, compost of shrub debris and sewage sludge on shrinkage behaviour and contact angle of till-derived loamy topsoil of a Haplic Luvisol under agricultural use. Novelty is the simultaneous determination of contact angle and shrinkage of soils amended with digestates composed of different composition in maize, sugar beet and winter wheat, compost of shrub debris and sewage sludge. The results suggest that the application of organic residues impacts the air capacity, while the contact angles remained in the subcritical range between > 0° and < 90°. The relationship between CA values and moisture ratios, ϑ, during proportional shrinkage was positive and linear (r2 of 0.98) and negative during residual- and zero-shrinkage (r2 of 0.93).
Hydrophobicity is a property of soils that reduces their affinity for water, which may help impeding the pressure build-up within aggregates, and reducing aggregate disruption. The purpose of this study was to examine the relation of soil hydrophobicity and drying temperature to water stability of aggregates while preventing the floating of dry aggregates using unhydrophobized and hydrophobized surface Andisol. Soil was hydrophobized using stearic acid into different hydrophobicities. Hydrophobicity was determined using sessile drop contact angle and water drop penetration time (WDPT). Water stability of aggregates (%WSA) was determined using artificially prepared model aggregates. The %WSA increased as the contact angle and WDPT increased. Contact angle and WDPT, which provided maximum %WSA showing less than 1 s of floating, was around 100° and 5 s, respectively. Although the %WSA gradually increased with increasing contact angle and WDPT above this level, high levels of hydrophobicity initiated aggregate floating, which would cause undesirable effects of water repellency. Heating at 50°C for 5 h d-1 significantly affected %WSA and hydrophobicity in hydrophobized samples, but did not in unhydrophobized samples. The results indicate that the contact angle and wetting rate (WDPT) are closely related with the water stability of aggregates. The results further confirm that high levels of hydrophobicities induce aggregate floating, and the drying temperature has differential effects on hydrophobicity and aggregate stability depending on the hydrophobic materials present in the soil.