The diurnal course of soil moisture as measured by various dielectric sensors: Effects of soil temperature and the implications for evaporation estimates

Soil moisture content, theta, of a bare and vegetated UK gravelly sandy loam soil (in situ and repacked in small lysimeters) was measured using various dielectric instruments (single-sensor ThetaProbes, multi-sensor Profile Probes, and Aquaflex Sensors), at depths ranging between 0.03 and I m, during the summers of 2001 (in situ soil) and 2002 (mini-lysimeters). Half-hourly values of evaporation, E, were calculated from diurnal changes in total soil profile water content, using the soil water balance equation. For the bare soil field, Profile Probes and ML2x ThetaProbes indicated a diurnal course of theta that did not concur with typical soil physical observations: surface layer soil moisture content increased from early morning until about midday, after which theta declined, generally until the early evening. The unexpected course of theta was positively correlated to soil temperature, T-s, also at deeper depths. Aquaflex and ML1 ThetaProbe (older models) outputs, however, reflected common observations: 0 increased slightly during the night (capillary rise) and decreased from the morning until late afternoon (as a result of evaporation). For the vegetated plot, the spurious diurnal theta fluctuations were less obvious, because canopy shading resulted in lower amplitudes of T-s. The unrealistic theta profiles measured for the bare and vegetated field sites caused diurnal estimates of E to attain downward daytime and upward night-time values. In the mini-lysimeters, at medium to high moisture contents, theta values measured by (ML2x) ThetaProbes followed a relatively realistic course, and predictions of E from diurnal changes in vertically integrated theta generally compared well with lysimeter estimates of E. However, time courses of theta and E became comparable to those observed for the field plots when the soil in the lysimeters reached relatively low values of theta. Attempts to correct measured theta for fluctuations in T, revealed that no generally applicable formula could be derived. (c) 2005 Elsevier B.V. All rights reserved.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.