Parameter estimation of a two-horizon soil profile by combining crop canopy and surface soil moisture observations using GLUE

Estimation of soil parameters by inverse modeling using observations on either surface soil moisture or crop variables has been successfully attempted in many studies, but difficulties to estimate root zone properties arise when heterogeneous layered soils are considered. The objective of this study was to explore the potential of combining observations on surface soil moisture and crop variables - leaf area index (LAI) and above-ground biomass for estimating soil parameters (water holding capacity and soil depth) in a two-layered soil system using inversion of the crop model STICS. This was performed using GLUE method on a synthetic data set on varying soil types and on a data set from a field experiment carried out in two maize plots in South India. The main results were (i) combination of surface soil moisture and above-ground biomass provided consistently good estimates with small uncertainity of soil properties for the two soil layers, for a wide range of soil paramater values, both in the synthetic and the field experiment, (ii) above-ground biomass was found to give relatively better estimates and lower uncertainty than LAI when combined with surface soil moisture, especially for estimation of soil depth, (iii) surface soil moisture data, either alone or combined with crop variables, provided a very good estimate of the water holding capacity of the upper soil layer with very small uncertainty whereas using the surface soil moisture alone gave very poor estimates of the soil properties of the deeper layer, and (iv) using crop variables alone (else above-ground biomass or LAI) provided reasonable estimates of the deeper layer properties depending on the soil type but provided poor estimates of the first layer properties. The robustness of combining observations of the surface soil moisture and the above-ground biomass for estimating two layer soil properties, which was demonstrated using both synthetic and field experiments in this study, needs now to be tested for a broader range of climatic conditions and crop types, to assess its potential for spatial applications. (C) 2012 Elsevier B.V. All rights reserved.

Crystal engineering: A brief overview

Crystal structures of organic and metal-organic compounds have been determined in enormous numbers over the past century, and at the time of writing this review, the Cambridge Structural Database has just crossed the half million mark. The possibility of designing a particular crystal packing is, however, of more recent origin and the subject of crystal engineering has addressed this possibility, more or less systematically, during the past 30 years. Crystal engineering demands a detailed and thorough knowledge of intermolecular interactions, which act as the supramolecular glue that binds molecules into crystals. It also requires systematic strategies for the design of a crystal, the architectural blueprint as it were. Finally, this enterprise needs to be geared towards a useful property in that the crystal that is being designed is a functional one. All these features of the subject are directly or indirectly connected with the fact that there is a very large database of known crystal structures that is available to the crystal engineer. This review attempts to briefly survey the current scenario in this expanding subject.

Estimation of soil hydraulic properties and their uncertainty: comparison between laboratory and field experiment

Often the soil hydraulic parameters are obtained by the inversion of measured data (e.g. soil moisture, pressure head, and cumulative infiltration, etc.). However, the inverse problem in unsaturated zone is ill-posed due to various reasons, and hence the parameters become non-unique. The presence of multiple soil layers brings the additional complexities in the inverse modelling. The generalized likelihood uncertainty estimate (GLUE) is a useful approach to estimate the parameters and their uncertainty when dealing with soil moisture dynamics which is a highly non-linear problem. Because the estimated parameters depend on the modelling scale, inverse modelling carried out on laboratory data and field data may provide independent estimates. The objective of this paper is to compare the parameters and their uncertainty estimated through experiments in the laboratory and in the field and to assess which of the soil hydraulic parameters are independent of the experiment. The first two layers in the field site are characterized by Loamy sand and Loamy. The mean soil moisture and pressure head at three depths are measured with an interval of half hour for a period of 1 week using the evaporation method for the laboratory experiment, whereas soil moisture at three different depths (60, 110, and 200 cm) is measured with an interval of 1 h for 2 years for the field experiment. A one-dimensional soil moisture model on the basis of the finite difference method was used. The calibration and validation are approximately for 1 year each. The model performance was found to be good with root mean square error (RMSE) varying from 2 to 4 cm(3) cm(-3). It is found from the two experiments that mean and uncertainty in the saturated soil moisture (theta(s)) and shape parameter (n) of van Genuchten equations are similar for both the soil types. Copyright (C) 2010 John Wiley & Sons, Ltd.

Neutral Nanosheets that Gel: Exfoliated Layered Double Hydroxides in Toluene

A simple strategy to exfoliate inorganic layered double hydroxide (LDH) solids to their ultimate constituent, intact single layers of nanometer thickness and micrometer size, is presented. The procedure involves intercalation of an ionic surfactant that forms a hydrophobic anchored surfactant bilayer in the galleries of the solid followed by simply stirring the intercalated solid in toluene. The method is rapid but at the same time gentle enough to produce exfoliated nanosheets of regular morphology that are electrically neutral and form stable gels at higher concentrations. In this Letter, we describe the phenomena and use molecular dynamics simulations to show that exfoliation of the LDH in toluene is a consequence of the modification of the cohesive dispersive interactions between surfactant chains anchored on opposing inorganic sheets by the toluene molecules. The toluene molecules function as a molecular glue, holding the surfactant-anchored LDH sheets together, leading to gel formation.

Sol-Gel Transition in Dispersions of Layered Double-Hydroxide Nanosheets

Surfactant-intercalated layered double-hydroxide solid Mg-Al LDH-dodecyl sulfate (DDS) undergoes rapid and facile delamination to its ultimate constituent, single sheets of nanometer thickness and micrometer size, in a nonpolar solvent such as toluene to form stable dispersions. The delaminated nanosheets are electrically neutral because the surfactant chains remain tethered to the inorganic layer even on exfoliation. With increasing volume fraction of the solid, the dispersion transforms from a free-flowing sol to a solidlike gel. Here we have investigated the sol-gel transition in dispersions of the hydrophobically modified Mg-Al LDH-DDS in toluene by rheology, SAXS, and (1)H NMR measurements. The rheo-SAXS measurements show that the sharp rise in the viscosity of the dispersion during gel formation is a consequence of a tactoidal microstructure formed by the stacking of the nanosheets with an intersheet separation of 3.92 nm. The origin and nature of the attractive forces that lead to the formation of the tactoidal structure were obtained from 1D and 2D (1)H NMR measurements that provided direct evidence of the association of the toluene solvent molecules with the terminal methyl of the tethered DDS surfactant chains. Gel formation is a consequence of the attractive dispersive interactions of toluene molecules with the tails of DDS chains anchored to opposing Mg-Al LDH sheets. The toluene solvent molecules function as molecular ``glue'' holding the nanosheets within the tactoidal microstructure together. Our study shows how rheology, SAXS, and NMR measurements complement each other to provide a molecular-level description of the sol-gel transition in dispersions of a hydrophobically modified layered double hydroxide.

Using long time series of agricultural-derived nitrates for estimating catchment transit times

The estimation of water and solute transit times in catchments is crucial for predicting the response of hydrosystems to external forcings (climatic or anthropogenic). The hydrogeochemical signatures of tracers (either natural or anthropogenic) in streams have been widely used to estimate transit times in catchments as they integrate the various processes at stake. However, most of these tracers are well suited for catchments with mean transit times lower than about 4-5 years. Since the second half of the 20th century, the intensification of agriculture led to a general increase of the nitrogen load in rivers. As nitrate is mainly transported by groundwater in agricultural catchments, this signal can be used to estimate transit times greater than several years, even if nitrate is not a conservative tracer. Conceptual hydrological models can be used to estimate catchment transit times provided their consistency is demonstrated, based on their ability to simulate the stream chemical signatures at various time scales and catchment internal processes such as N storage in groundwater. The objective of this study was to assess if a conceptual lumped model was able to simulate the observed patterns of nitrogen concentration, at various time scales, from seasonal to pluriannual and thus if it was relevant to estimate the nitrogen transit times in headwater catchments. A conceptual lumped model, representing shallow groundwater flow as two parallel linear stores with double porosity, and riparian processes by a constant nitrogen removal function, was applied on two paired agricultural catchments which belong to the Research Observatory ORE AgrHys. The Global Likelihood Uncertainty Estimation (GLUE) approach was used to estimate parameter values and uncertainties. The model performance was assessed on (i) its ability to simulate the contrasted patterns of stream flow and stream nitrate concentrations at seasonal and inter-annual time scales, (ii) its ability to simulate the patterns observed in groundwater at the same temporal scales, and (iii) the consistency of long-term simulations using the calibrated model and the general pattern of the nitrate concentration increase in the region since the beginning of the intensification of agriculture in the 1960s. The simulated nitrate transit times were found more sensitive to climate variability than to parameter uncertainty, and average values were found to be consistent with results from others studies in the same region involving modeling and groundwater dating. This study shows that a simple model can be used to simulate the main dynamics of nitrogen in an intensively polluted catchment and then be used to estimate the transit times of these pollutants in the system which is crucial to guide mitigation plans design and assessment. (C) 2015 Elsevier B.V. All rights reserved.

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.