In structured soils, interaction of percolating water and reactive solutes with the soil matrix is often restricted to the outer surfaces of the preferential flow paths. Such surfaces of soil aggregates and biopores are mostly covered by organic matter (OM) that finally controls wettability, sorption, and transfer properties of the flow pathways. However, the local OM properties along such surfaces are largely unknown to date because the coatings are relatively thin and vulnerable. The objective of this study was to determine and compare the local two‐dimensional distribution of soil OM composition at intact aggregate surfaces that serve as preferential flow paths. The Fourier transformed infrared spectroscopy in diffuse reflectance mode (diffuse reflectance infrared Fourier transform, DRIFT) was applied to determine transects and grids of OM functional group data (i.e., CH/CO ratios) on undisturbed and intact surfaces of soil aggregate samples using a DRIFT mapping procedure in 1‐mm steps. The aggregate sample surfaces could be distinguished by DRIFT mapping in areas from earthworm burrows, root channels, and aggregate coatings. The water drop infiltration time of these structural surfaces appeared to correspond with CH/CO ratios for uncoated crack surfaces but less so for earthworm burrows. The results show that coatings at preferential flow‐path surfaces differed locally in terms of OM composition, distribution, and possibly also in wettability, indicating yet unknown implications for preferential movement of water and reactive solutes.

Soil dust particles emitted from agricultural areas contain considerable mass fractions of organic material. Also, soil dust particles may act as carriers for potentially ice‐active biological particles. In this work, we present ice nucleation experiments conducted in the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber. We investigated the ice nucleation efficiency of four types of soil dust from different regions of the world. The results are expressed as ice nucleation active surface site (INAS) densities and presented for the immersion freezing and the deposition nucleation mode. For immersion freezing occurring at 254 K, samples from Argentina, China, and Germany show ice nucleation efficiencies which are by a factor of 10 higher than desert dusts. On average, the difference in ice nucleation efficiencies between agricultural and desert dusts becomes significantly smaller at temperatures below 247 K. In the deposition mode the soil dusts showed higher ice nucleation activity than Arizona Test Dust over a temperature range between 232 and 248 K and humidities RHice up to 125%. INAS densities varied between 109 and 1011 m−2 for these thermodynamic conditions. For one soil dust sample (Argentinian Soil), the effect of treatments with heat was investigated. Heat treatments (383 K) did not affect the ice nucleation efficiency observed at 249 K. This finding presumably excludes proteinaceous ice‐nucleating entities as the only source of the increased ice nucleation efficiency.

Structured subsoil horizons are characterized by biopores and shrinkage cracks, which may serve as preferential flow paths. The surfaces of cracks and biopores may be coated by clay-organic material. The spatiallydistributed organic matter (OM) composition at such structural surfaces was studied at the millimetre scale using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in the mid-infrared range (MIR). Intact biopores such as earthworm burrows and root channels, and crack surfaces of nine subsoil horizons were analysed. The samples were from arable and forest Luvisols, one Regosol, one Stagnosol and Cambisols developed from loess, till, mudstone and limestone. For better comparison between soils, the DRIFT signal intensities were corrected for the particle-size effects. The OM was characterized by the ratio between alkyl-(C-H) and carbonyl (C=O) functional groups (C-H/C=O), which represent an index of the potential wettability (PWI) of the OM. The PWI was larger for biopores than for crack surfaces and the soil matrix, indicating a smaller potential wettability of OM at biopore surfaces. The millimetre-scale spatial variability of OM was especially large for the surfaces of root channels. Samples from till-derived Luvisols had smaller PWI (with greater potential wettability than surfaces from loess-derived Luvisols) than other soil types. The mean PWI of the arable Luvisol crack surfaces was less than that of the forest Luvisol samples. The results suggest that the spatial distribution of OM properties at intact structural surfaces may be important for describing sorption and mass transfer processes during preferential flow.

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Vegetation and its succession can change the parameters of soil water repellency (SWR) due to the change in amount and composition of soil organic matter. This hypothesis was tested in natural and agricultural environments in Germany, Hungary, and Slovakia. The parameters investigated were the extent (determined by the repellency indices RI, RIc, and RIm) and persistence (determined by the water drop penetration time and water repellency cessation time) of SWR, as well as the potential wettability index of organic matter in sandy soils. The SWR parameters and soil organic carbon (SOC) content increased in the course of primary succession at Mehlinger Heide, Germany, and Sekule, Slovakia. Dye tracer experiments undertaken at Sekule revealed contrasting flow patterns: (a) preferential flow in water‐repellent soil under biological soil crust and grass and (b) piston flow in wettable soil that consists almost of pure quartz sand. The effective flow cross section decreased, and the degree of preferential flow increased in the course of primary succession at Sekule. No consistent trend of the SWR parameters and SOC was observed in the course of secondary succession at Csólyospálos, Hungary. This is the first time that differences between trends in SWR parameters due to primary and secondary successions were observed and related to the composition of SOC and extracellular polymeric substances. It can be concluded that dynamics of soil organic matter composition during the succession controls SWR.

The organic matter (OM) in biopore walls and aggregate coatings may be important for sorption of reactive solutes and water as well as for solute mass exchange between the soil matrix and the preferential flow (PF) domains in structured soil. Structural surfaces are coated by illuvial clay‐organic material and by OM of different origin, e.g., earthworm casts and root residues. The objectives were to verify the effect of OM on wettability and infiltration of intact structural surfaces in clay‐illuvial horizons (Bt) of Luvisols and to investigate the relevance of the mm‐scale distribution of OM composition on the water and solute transfer. Intact aggregate surfaces and biopore walls were prepared from Bt horizons of Luvisols developed from Loess and glacial till. The mm‐scale spatial distribution of OM composition was scanned using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The ratio between alkyl and carboxyl functional groups in OM was used as potential wettability index (PWI) of the OM. The infiltration dynamics of water and ethanol droplets were determined measuring contact angles (CA) and water drop penetration times (WDPT). At intact surfaces of earthworm burrows and coated cracks of the Loess‐Bt, the potential wettability of the OM was significantly reduced compared to the uncoated matrix. These data corresponded to increased WDPT, indicating a mm‐scaled sub‐critical water repellency. The relation was highly linear for earthworm burrows and crack coatings from the Loess‐Bt with WDPT > 2.5 s. Other surfaces of the Loess‐Bt and most surfaces of the till‐derived Bt were not found to be repellent. At these surfaces, no relations between the potential wettability of the OM and the actual wettability of the surface were found. The results suggest that water absorption at intact surface structures, i.e., mass exchange between PF paths and soil matrix, can be locally affected by a mm‐scale OM distribution if OM is of increased content and is enriched in alkyl functional groups. For such surfaces, the relation between potential and actual wettability provides the possibility to evaluate the mm‐scale spatial distribution of wettability and sorption and mass exchange from DRIFT spectroscopic scanning.

In the clay‐illuvial horizons (Bt) of Luvisols, surfaces of biopores and aggregates can be enriched in clay and organic matter (OM), relative to the bulk of the soil matrix. The OM composition of these coatings determines their bio‐physico‐chemical properties and is relevant for transport and transformation processes but is largely unknown at the molecular scale. The objective of this study was to improve the interpretation of spectra from Fourier transform infrared spectroscopy in diffuse reflectance mode (DRIFT) by using thermograms and released ion intensities obtained with pyrolysis‐field ionization mass spectrometry (Py‐FIMS) for a more detailed analysis of the mm‐scale spatial distribution of OM components at intact structural surfaces. Samples were separated from earthworm burrow walls, crack coatings, uncoated cracks, root channels, and pinhole fillings of the Bt‐horizons of Luvisols. The information from Py‐FI mass spectra enabled the assignment of OM functional groups also from spectral regions of overlapping DRIFT signal intensities to specific OM compound classes. In particular, bands from C=O and C=C bonds in the infrared range of wave numbers between 1,641 and 1,605 cm−1 were related to heterocyclic N‐compounds, benzonitrile, and naphthalene. The OM at earthworm burrow walls was composed of chemically labile aliphatic C‐rich and rather stable lignin and alkylaromatic compounds whereas the OM of thick crack coatings and pinholes was dominated by heterocyclic N and nitriles and high‐molecular compounds, likely originating from combustion residues. In combination with Py‐FIMS, DRIFT applications to intact samples seem promising for generating a more detailed mm‐scale spatial distribution of OM‐related sorption and wettability properties of crack and biopore surfaces that may serve as preferential flow paths in structured soils.

Fourier‐transformed infrared spectroscopy in diffuse reflectance mode (DRIFT) has been proposed as a tool for the characterization of organic matter (OM) composition at intact soil surfaces; however, the local properties and the geometry of intact structural surfaces (e.g., biopores and cracks) affect the reflection in as yet unknown ways. Our goal was to develop an approach to correct for surface geometry effects. The objectives were to analyze the effects of (i) particle size, (ii) porosity, and (iii) specific surface shapes on the infrared signal intensity by comparing measured with simulated reflectance data. Mid‐infrared DRIFT spectra were obtained from differently textured quartz samples and from gypsum blocks with defined surface shapes as models for soil porous systems. A beam tracing model (BTM) was used for the numerical description of the infrared beam propagation in such model soils. The measured DRIFT signal intensity and the simulated bihemispherical reflectance both decreased with increasing quartz particle size; the resolution of the DRIFT spectra decreased with particle size. The geometric effects of the microtopography can be explained by the local variations in the distance between the collection mirror of the DRIFT device and the sample surface. The DRIFT‐measured effects of particle size and surface topography on the signal intensity agreed with the BTM simulation results. The results suggest that a radiative transfer model is useful for interpretations of DRIFT data obtained at intact structural surfaces. The OM properties can be analyzed with DRIFT for surfaces that consist of particles <70 μm and have relatively small, i.e., <1‐mm, relief differences.