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Highlights• We introduce a new technique that allows measuring water repellency of individual particles • Two variants of the method each provide relatively simple and quick wettability assessments • It showed naturally wettable bulk soils contained water repellent particles and vice versa

New approaches to the study of hydrophobicity and wetting of soils were investigated with the following research objectives: 1) to evaluate the use of fluorescence probes, nile red and pyrene, as tools to assess the polarity and viscosity of organics adsorbed to soils; 2) to assess, using a variety of kinetic methods, what steps are involved in wetting soils; and 3) to assess the validity of current theories for the anomalously high contact angles often measured for water on soils, and investigate an alternative explanation based on the geometry of a water drop sitting on hydrophobic particles. Whilst it was possible to image nile red emission after adsorption to soils, issues of emission intensity and soil auto-luminescence suggest that nile red is not a useful probe for soil studies. Fluorescence measurements were made using pyrene as an in-situ polarity and viscosity/mobility probe. Using pyrene co-deposited with organics on acid-washed sand, excimer kinetics showed a decrease in environment mobility as the organic layer was changed from a liquid to a hard wax. Spectra from natural soils indicated varying environmental polarity and heterogeneity within the soil samples studied. A theoretical model for soil wetting, involving adhesional-immersional wetting followed by branching capillary wetting, is proposed, and a series of experiments to assess the validity of this model described. Methods used include: water drop penetration time (WDPT) test, mass of soil grains wetted over time; time taken for penetration of a water drop into different soil thicknesses; optical microscopy; WDPT measurements with salt solutions of different densities. An alternative interpretation of the anomalously high contact angles measured on soils is proposed based on a correction factor for water on particles. To assess this, measurements were made using regularly arranged ballpoint needles and metal spheres, and acid-washed sand and natural soil, coated in paraffin wax. .

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Soil water repellency, that is, the reduced ability of soils to absorb water, is thought to be caused by organic coatings with predominantly non‐polar properties on soil particle surfaces. Given the important role of particle surface polarity in determining soil water repellency, we explored the use of fluorescent probes as a method for the direct in‐situ determination of the distribution and polarity of organics on bulk soil surfaces, and of their molecular mobility. We used nile red and pyrene, which have both been used successfully as environmental probes in previous studies, but have not been applied before to bulk soils. The probes were either (a) co‐deposited with other organics known to induce water‐repellent behaviour with acid‐washed sand to produce ‘model soils’ or (b) adsorbed directly onto sandy soils that were naturally water repellent to different degrees, and studied using fluorescence microscopy and steady‐state and time‐resolved fluorescence. Reliable measurements could be made using pyrene as an in‐situ probe on both model and natural soils, and a viscosity/mobility probe on model soils, whereas nile red was found not to be a useful probe. On model soils, made using hexadecane (HEX), octadecane (OCT) or stearic acid (SA) on acid‐washed sand, pyrene excimer formation kinetics showed a decrease in environment mobility as the organic layer changes from a liquid through to a hard wax. Spectra from pyrene adsorbed to natural soils indicated varying environmental polarity and heterogeneity within the soil samples studied. Highlights Exploration of in‐situ fluorescent probes to study polarity and viscosity of organics on soils. Fluorescent probes have never been used in situ on bulk soils before. Pyrene probe shows variation in mobility, polarity and heterogeneity of organics on soils. Pyrene is a useful in‐situ fluorescent probe of polarity and mobility of organics on soils.