[1] The commonly used hydraulic models only account for capillary water retention and conductivity. Adsorptive water retention and film conductivity is neglected. This leads to erroneous description of hydraulic properties in the dry range. The few existing models, which account for film conductivity and adsorptive retention are either difficult to use or physically inconsistent. A new set of empirical hydraulic models for an effective description of water dynamics from full saturation to complete dryness is introduced. The models allow a clear partitioning between capillary and adsorptive water retention as well as between capillary and film conductivity. The number of adjustable parameters for the new retention model is not increased compared to the commonly used models, whereas only one extra parameter for quantifying the contribution of film conductivity is required for the new conductivity model. Both models are mathematically simple and thus easy to use in simulation studies. The new liquid conductivity model is coupled with an existing vapor conductivity model to describe conductivity in the complete moisture range. The new models were successfully applied to literature data, which all reach the dry to very dry range and cannot be well described with the classic capillary models. The investigated soils range from pure sands to clay loams. A simulation study with steady-state water transport scenarios shows that neglecting either film or vapor conductivity or both can lead to significant underestimation of water transport at low water contents.

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[1] The commonly used models for characterizing hydraulic conductivity of porous media rely on pore bundle concepts that account for capillary flow only and neglect film flow. Experimental evidence suggests that water flow at medium to low water contents in unsaturated porous media can be significantly underestimated by these capillary bundle models. We present a new model that combines a simple film flow function with the capillary flow model of Mualem. This new model can easily be coupled to any water retention function. Moreover, due to its mathematical simplicity, it can easily and efficiently be implemented in existing codes for the numerical solution of unsaturated flow problems. We investigated a set of soil water retention and conductivity data from the literature that all reached dry conditions and were poorly described by existing capillary bundle models. These data were well described with the new model if the model was coupled with an appropriate retention function. Investigation of conductivity data from the UNsaturated SOil hydraulic DAtabase (UNSODA) database showed that, in 75% of all data sets, the new model achieved the best performance using a modified version of Akaike's information criterion. The numeric simulation of an evaporation scenario using Richards's equation showed that by neglecting film flow, the evaporation rate may be underestimated by more than an order of magnitude.Citation: Peters, A., and W. Durner (2008), A simple model for describing hydraulic conductivity in unsaturated porous media accounting for film and capillary flow, Water Resour. Res., 44, W11417,

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Nanoparticles enter soils through various pathways. In the soil, they undergo various interactions with the solution and the solid phase. We tested the following hypotheses using batch experiments: i) the colloidal stability of Ag NP increases through sorption of soil-borne dissolved organic matter (DOM) and thus inhibits aggregation; ii) the presence of DOM suppresses Ag oxidation; iii) the surface charge of Ag NP governs sorption onto soil particles. Citrate-stabilized and bare Ag NPs were equilibrated with (colloid-free) soil solution extracted from a floodplain soil for 24h. Nanoparticles were removed through centrifugation. Concentrations of free Ag ions and DOC, the specific UV absorbance at a wavelength of 254 nm, and the absorption ratio α254/α410 were determined in the supernatant. Nanoparticle aggregation was studied using time-resolved dynamic light scattering (DLS) measurement following the addition of soil solution and 1.5mM Ca(2+) solution. To study the effect of surface charge on the adsorption of Ag NP onto soil particles, bare and citrate-stabilized Ag NP, differing in the zeta potential, were equilibrated with silt at a solid-to-solution ratio of 1:10 and an initial Ag concentration range of 30 to 320 μg/L. Results showed that bare Ag NPs sorb organic matter, with short-chained organic matter being preferentially adsorbed over long-chained, aromatic organic matter. Stabilizing effects of organic matter only come into play at higher Ag NP concentrations. Soil solution inhibits the release of Ag(+) ions, presumably due to organic matter coatings. Sorption to silt particles was very similar for the two particle types, suggesting that the surface charge does not control Ag NP sorption. Besides, sorption was much lower than in comparable studies with sand and glass surfaces.

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