Entire Range Of Water Content Research Articles

Water-induced changes in choline chloride-carboxylic acid deep eutectic solvents properties

Deep eutectic solvents (DES) have become a promising alternative to molecular organic solvents and ionic liquids in a variety of scientific applications. Their customizable physicochemical properties make them attractive for extraction, catalysis, electrochemistry and drug delivery. Recently, the study of not so much DES themselves, as their mixtures with water, has attracted particular interest. In this study, six widely used DESs based on choline chloride and carboxylic acids (citric, tartaric, malic, glycolic, malonic and lactic) with a water content of 0–50 wt% were analyzed. Properties such as density, viscosity, conductivity and spectral properties of DES (IR spectroscopy and refractive index) were studied. The results show that in the entire range of water content under study, there are no abrupt changes in properties for all the studied parameters, which allows us to conclude that water is gradually incorporated into the DES structure without its destruction. However, within this class of eutectic solvents, subclasses can be distinguished, due to various changes in the studied properties. These results provide important information for optimizing the performance of DES in practical applications and highlight their potential as sustainable green solvents in modern science and technology.

HYPROP-FIT to Model Rock Water Retention Curves Estimated by Different Methods

The water retention curve, which relates the matric potential, ψ, to the water content, θ, is essential to describe the flow processes in the unsaturated zone and provides useful information for environmental and engineering applications. There are few studies devoted to measuring the rock water retention curves due to the rock’s tightness, which makes it more technically difficult to use specific methods. In this study, we tested four different methods to measure water retention curves of two lithotypes of carbonate porous rocks with the aim to find the most effective to be applied to rock samples. Suction table, evaporation, Quasi-Steady Centrifuge, and WP4-T dewpoint potentiameter methods have been applied. The Quasi-Steady Centrifuge method proved to be the only one capable of determining water retention curves in the entire water content range and capturing the bimodality of the tested media with respect to the other methods. The measured water retention data were fitted with HYPROP-FIT software that allows us to accurately describe the WRCs and obtain critical parameters for the numerical simulation of flow and transport through the vadose zone, which plays a key role in various environmental issues.

Forest soil penetration resistance following heavy traffic: A 10‐year field study

AbstractNatural recovery of acidic soils following heavy traffic is assumed to take several decades. The aim of this study was to monitor the recovery of soil penetration resistance (PR) after soil compaction by heavy traffic at two forest sites. The sites, located in northeast France, have soils that differ slightly in pH and silt content. The impact on soil PR following heavy traffic was dependent on the soil water content (WC) at the time of measurement, and, therefore, the entire WC range and corresponding PR values were measured. For the most acidic and silty soil, no difference in PR among treatments was observed when the soils were near saturation; however, the difference in PR values was high when soils were close to wilting point. For the least acidic and silty soil, the impact of heavy traffic on PR could be detected whatever the soil moisture, with the magnitude of the effect dependent on the soil water content and depth considered. Standardized PR values with regard to WC allowed an analysis of the evolution of the effect of heavy traffic with time. Ten years after being subjected to heavy traffic, the PR values in the 0‐ to 40‐cm layer recovered to undisturbed values at the least acidic and silty site, but not WC dynamic. The most acidic and silty soil site did not show any recovery of PR or WC dynamic ten years following traffic, although liming at this site was able to increase the regeneration of PR to undisturbed levels.

Conformational transition of polyelectrolytes in mixed solvent by dielectric spectroscopy: Electrostatic and hydrophobic interactions

ABSTRACTWe studied conformational transition of poly(acrylic acid)‐graft‐dodecyl (PAA‐g‐dodecyl), and PAA‐graft‐poly(ethylene oxide)‐graft‐dodecyl (PAA‐g‐PEO‐g‐dodecyl) molecules in DMF/H2O solvent by dielectric analysis method utilizing a double‐layer polarization theory. In addition to the hydrophobic interaction which has been demonstrated to be vital for their conformational transition with water content, it is confirmed that the electrostatic interaction is crucial. For PAA‐g‐dodecyl molecules, at a critical value of water content, a peak value of correlation length is reached originating from the delicate balance between electrostatic and hydrophobic interactions. For PAA‐g‐PEO‐g‐dodecyl molecules, chains conformation is mainly determined by electrostatic interaction over the entire range of water content due to the low content of dodecyl groups. Meanwhile, H‐bond associative interaction prevents the dissociation of free carboxyl groups over the range of lower water content, thus their stretched transition moves to higher water content. Our results provide the underlying insights needed to understand solvent effect on the conformational transition for polyelectrolytes with hydrophobic groups. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1716–1724

A fractal-based model for soil water characteristic curve over entire range of water content

Soil water characteristic curve (SWCC) has been an important role in hydraulic engineering, civil engineer and petroleum engineering, etc. Most of SWCC models neglected the film flow in the dry state, so that they cannot accurately describe the SWCC over entire range of water content. In this work, an alternative fractal model is proposed to predict the SWCC over entire range of water content by combining Campbell and Shiozawa model and Tao model. The proposed model can well predict twelve sets of experimental data, and its parameters, including the fractal dimension, the saturated volumetric water content, the matric suction at oven-dry condition, and the air-entry value, accord with theoretical value. The results show that there is a strong linear relationship between volumetric water content and matrix suction in log-log scale for different fractal pore-size distribution of soils. In addition, good agreement is obtained between the experimental data and the model predictions in all of the cases. Cited as : Jin, T., Cai, X., Chen, Y., Jiang, S., Wei, W. A fractal-based model for soil water characteristic curve over entire range of water content. Capillarity, 2019, 2(4): 66-75, doi: 10.26804/capi.2019.04.02

The influence of H2O and SiO2 on the structure of silicoborate glasses

To understand the impact of dissolved water on structure and properties, four boron-rich glasses of molar compositions 15-x Na2O x CaO 15 SiO2 70 B2O3 (with x = 0, 7.5, 10) and 10 Na2O 15 SiO2 75 B2O3 were prepared and subsequently hydrated (up to 8 wt% H2O). Density measurements show a non-linear trend upon hydration implying large structural changes in particular at water contents <2 wt%. Near-infrared spectroscopy shows hydroxyl groups are the dominant species in all glasses upon the entire range of water content. Molecular H2O is detectable only at total water contents >2 wt%. 11B MAS NMR spectra show that the abundance of BO4 species is mainly controlled by ratio of (Na2O + CaO)/B2O3 while incorporation of water plays a minor role. Compared to borate glasses, the efficiency of formation of BO4 tetrahedra is favored by crosslinking of the network by SiO4-units. The glass transition temperatures, determined by differential thermal analysis, decreases continuously with water content due to breakage of B-O-B bonds by hydrolysis. However, compared to silicates and aluminosilicates, the effect of dissolved water is less pronounced which can be explained by weaker B-O-B bonds in comparison to Si-O-Si bonds.

α-chymotrypsin in water-acetone and water-dimethyl sulfoxide mixtures: Effect of preferential solvation and hydration.

We investigated water/organic solvent sorption and residual enzyme activity to simultaneously monitor preferential solvation/hydration of protein macromolecules in the entire range of water content at 25°C. We applied this approach to estimate protein destabilization/stabilization due to the preferential interactions of bovine pancreatic α-chymotrypsin with water-acetone (moderate-strength H-bond acceptor) and water-DMSO (strong H-bond acceptor) mixtures. There are three concentration regimes for the dried α-chymotrypsin. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity values are close to 100%. At intermediate water content, the dehydrated α-chymotrypsin has a higher affinity for acetone/DMSO than for water. Residual enzyme activity is minimal in this concentration range. The acetone/DMSO molecules are preferentially excluded from the protein surface at the lowest water content, resulting in preferential hydration. The residual catalytic activity in the water-poor acetone is ∼80%, compared with that observed after incubation in pure water. This effect is very small for the water-poor DMSO. Two different schemes are operative for the hydrated enzyme. At high and intermediate water content, α-chymotrypsin exhibits preferential hydration. However, at intermediate water content, in contrast to the dried enzyme, the initially hydrated α-chymotrypsin possesses increased preferential hydration parameters. At low water content, no residual enzyme activity was observed. Preferential binding of DMSO/acetone to α-chymotrypsin was detected. Our data clearly demonstrate that the hydrogen bond accepting ability of organic solvents and the protein hydration level constitute key factors in determining the stability of protein-water-organic solvent systems.

Preferential Solvation/Hydration of α-Chymotrypsin in Water-Acetonitrile Mixtures.

The aim of our study is to monitor the preferential hydration/solvation of the protein macromolecules at low and high water content in water-organic mixtures. Our approach is based on the analysis of the absolute values of the water/organic solvent sorption. We applied this approach to estimate the protein stabilization/destabilization due to the preferential interactions of α-chymotrypsin with water-acetonitrile mixtures. At high water content, α-chymotrypsin is preferentially hydrated. At the intermediate water content, the preferential interaction changed from preferential hydration to preferential binding of acetonitrile. From infrared spectra, changes in the structure of α-chymotrypsin were determined through an analysis of the structure of the amide I band. Acetonitrile augments the intensity of the 1626 cm-1 band assigned to the intermolecular β-sheet aggregates. At low water content, the protein is in a glassy (rigid) state. The H-bond accepting acetonitrile molecules are not effective in solvating the dehydrated protein molecules alone. Therefore, the acetonitrile molecules are preferentially excluded from the protein surface, resulting in the preferential hydration. Advantages of our approach: (i) The preferential interaction parameters can be determined in the entire range of water content in water-organic mixtures. (ii) Our approach facilitates the individual evaluation of the Gibbs energies of water, protein, and organic solvent.

Application of a Multi-Scale form of Terzaghi’s Effective Stress Principle for Unsaturated Expansive Clays to Simulate Hydro-Mechanical Behavior During Hydration

Our recently developed multi-scale form of Terzaghi’s effective stress principle for unsaturated swelling clays that was rigorously derived by periodic homogenization starting from micro- and nano-mechanical analyses is applied to numerically simulate one-dimensional swelling pressure tests of compacted bentonites during hydration. The total macroscopic stress captures the coupling between disjoining forces at the nanoscopic scale of clay platelets and capillary effects at the microscopic scale of clay aggregates over the entire water content range. The numerical results allow to draw conclusions on the water transfer mechanism between inter- and intra-aggregate pores during hydration and consequently on the evolution of the external swelling pressure resulting from the competition between capillary and disjoining forces. In addition, such application highlights the abilities and the limits of the electrical double-layer theory to compute the disjoining pressure in the nano-pores. For large platelet distances, in the range of osmotic swelling, the nature of the disjoining pressure is electro-chemical and can be computed from Poisson-Boltzmann theory. Conversely, at small distances, in the crystalline swelling, a solvation component has to be added to account for the molecular nature of the solvent. As a first improvement of the nano-scale description the solvent is treated as a hard sphere fluid using Density Functional Theory.

Extrapolative capability of two models that estimating soil water retention curve between saturation and oven dryness.

Accurate estimation of soil water retention curve (SWRC) at the dry region is required to describe the relation between soil water content and matric suction from saturation to oven dryness. In this study, the extrapolative capability of two models for predicting the complete SWRC from limited ranges of soil water retention data was evaluated. When the model parameters were obtained from SWRC data in the 0–1500 kPa range, the FX model (Fredlund and Xing, 1994) estimations agreed well with measurements from saturation to oven dryness with RMSEs less than 0.01. The GG model (Groenevelt and Grant, 2004) produced larger errors at the dry region, with significantly larger RMSEs and MEs than the FX model. Further evaluations indicated that when SWRC measurements in the 0–100 kPa suction range was applied for model establishment, the FX model was capable of producing acceptable SWRCs across the entire water content range. For a higher accuracy, the FX model requires soil water retention data at least in the 0- to 300-kPa range to extend the SWRC to oven dryness. Comparing with the Khlosi et al. (2006) model, which requires measurements in the 0–500 kPa range to reproduce the complete SWRCs, the FX model has the advantage of requiring less SWRC measurements. Thus the FX modeling approach has the potential to eliminate the processes for measuring soil water retention in the dry range.

Modelling the compaction curve of fine-grained soils

A theoretical model for the compaction curve of fine-grained soils at various compaction efforts for the entire range of water content is presented in this study. The prediction method is based on the assumption that the compaction curve represents the state surface at the yield state in an unsaturated condition. Thus, for each applied compaction effort, the compaction curve relates to one yielding point on the saturated normal consolidation line (NCL). For a given soil, the model requires the NCL, Src, and one point from any compaction curve to predict the compaction curves for different compaction efforts. Moreover, the lines of equal suctions on the compaction curves can be determined if the SWCC, the wetting path, is known. The model introduced here provides additional theoretical understanding of the soil׳s volume change behavior of the compaction curve. The model was verified in two ways: first it was verified quantitatively, by experimental results, and second it was verified qualitatively, by examining the relationships from other models in the literature. The model was further applied to experimental data reported in the literature on previous static and dynamic compaction tests. The results show that the model fits the experimental data very well. Finally, a simple chart, based on this model and using only liquid limits, is presented to estimate γdmax and OMC quickly.

A study of the hydration of ribonuclease A using isothermal calorimetry

This work is part of a systematic study undertaken to find the excess thermodynamic functions of binary protein–water systems. Isothermal calorimetry and water sorption measurements were applied to characterize the hydration dependencies of the excess thermodynamic functions. The advantages of our methodology are (i) we are able to simultaneously determine the excess partial quantities of water and proteins; (ii) these thermodynamic quantities can be determined in the entire range of water content. Here, in particular, the excess partial enthalpies of water and bovine pancreatic ribonuclease A (RNase A) have been determined. The excess partial enthalpies for RNase A are compared with the published data for several unrelated globular proteins (lysozyme, chymotrypsinogen A, serum albumin, lactoglobulin). These biomacromolecules represent a series of proteins in which the hydrophobicity of proteins is gradually changed in a wide range. It was found that the excess partial quantities for the studied proteins are determined by the hydration of the hydrophilic and hydrophobic protein groups. The more hydrophilic a protein, the more significant a hydrophilic hydration contribution is and vice versa. RNase A is the most hydrophilic protein under the study. This protein has the most significant hydrophilic hydration contribution. Lactoglobulin is the most hydrophobic protein under the study. This protein has the most significant hydrophobic hydration contribution.

Hydration of Proteins: Excess Partial Volumes of Water and Proteins

High precision densitometry was applied to study the hydration of proteins. The hydration process was analyzed by the simultaneous monitoring of the excess partial volumes of water and the proteins in the entire range of water content. Five unrelated proteins (lysozyme, chymotrypsinogen A, ovalbumin, human serum albumin, and β-lactoglobulin) were used as models. The obtained data were compared with the excess partial enthalpies of water and the proteins. It was shown that the excess partial quantities are very sensitive to the changes in the state of water and proteins. At the lowest water weight fractions (w(1)), the changes of the excess functions can mainly be attributed to water addition. A transition from the glassy to the flexible state of the proteins is accompanied by significant changes in the excess partial quantities of water and the proteins. This transition appears at a water weight fraction of 0.06 when charged groups of proteins are covered. Excess partial quantities reach their fully hydrated values at w(1) > 0.5 when coverage of both polar and weakly interacting surface elements is complete. At the highest water contents, water addition has no significant effect on the excess quantities. At w(1) > 0.5, changes in the excess functions can solely be attributed to changes in the state of the proteins.

Hydration of Proteins: Excess Partial Enthalpies of Water and Proteins

Isothermal batch calorimetry was applied to study the hydration of proteins. The hydration process was analyzed by the simultaneous monitoring of the excess partial enthalpies of water and the proteins in the entire range of water content. Four unrelated proteins (lysozyme, chymotrypsinogen A, human serum albumin, and β-lactoglobulin) were used as models. The excess partial quantities are very sensitive to the changes in the state of water and proteins. At the lowest water weight fractions (w(1)), the changes of the excess thermochemical functions can mainly be attributed to water addition. A transition from the glassy to the flexible state of the proteins is accompanied by significant changes in the excess partial quantities of water and the proteins. This transition appears at a water weight fraction of 0.06 when charged groups of proteins are covered. Excess partial quantities reach their fully hydrated values at w(1) > 0.5 when coverage of both polar and weakly interacting surface elements is complete. At the highest water contents, water addition has no significant effect on the excess thermochemical quantities. At w(1) > 0.5, changes in the excess functions can solely be attributed to changes in the state of the proteins.

Hydration of α-chymotrypsin: Excess partial enthalpies of water and enzyme

A novel method has been developed for studying simultaneously the excess partial enthalpies of water and the enzyme in the entire range of water content. Bovine pancreatic α-chymotrypsin was used as a model enzyme. The proposed method includes the measurements of the enthalpies of solution of the dried and hydrated enzyme in water at 25 °C. From these thermochemical data the excess partial enthalpies of water and α-chymotrypsin were calculated. The partial quantities are very sensitive to the changes in the state of water and α-chymotrypsin. A transition from the glassy to the flexible state of α-chymotrypsin is accompanied by significant changes in the excess partial enthalpies of water and α-chymotrypsin. This transition appears at water weight fraction ( w 1) of 0.06 when charged groups of α-chymotrypsin are covered. Excess partial quantities reach their fully hydrated values at w 1 > 0.4 when coverage of both polar and weakly interacting surface elements is complete.

Modeling rehydration of porous food materials: I. Determination of characteristic curve from water sorption isotherms

Scarce use of physically based models for simulating foodstuff rehydration is related, inter alia, to difficulties in determining their hydraulic characteristic curve (water content vs. matric potential under equilibrium conditions). Its direct determination is not feasible for foodstuffs as it requires extended contact time with water to reach equilibrium that may cause microbial spoilage, swelling and physical destruction of the sample. To circumvent these difficulties, an alternative indirect method for determining the characteristic curve over the entire water-content range is proposed. It is based on the hypothesis that the end-parts of this curve, the air-entry value and saturated water content for the wet-end and water sorption isotherm for the dry-end, are relatively easily determined. The predicted characteristic curve was successfully verified for a model food material by comparing it with an independently measured values. Then, it was utilized for simulated rehydration by solving the Richards equation.

Complex Permittivity Model for Time Domain Reflectometry Soil Water Content Sensing: I. Theory

Despite numerous applications of time‐domain reflectometry (TDR), serious difficulties remain in estimating accurate soil water contents under field conditions, especially in fine‐textured soils. We developed a physically based calibration model to predict the frequency‐ and temperature‐dependent complex dielectric response of soils. The model was used to predict frequency‐dependent attenuation and a single “effective” frequency approximation of apparent permittivity of the soil. Effective frequency was predicted to decline from 450 to 160 MHz as water contents increased from air dry to saturation. Predicted frequency decline was small for an input bandwidth of 130 MHz, reflecting that modeled polarization mechanisms associated with relaxation frequencies above 100 MHz were responsible for most of the frequency‐dependent attenuation. For specific surface areas ranging from 150 to 300 m2 g−1, simulations indicate that ignoring dielectric and conductive losses or the associated decline in effective frequency results in a 5 to 22% underestimation of the apparent permittivity. Both the power‐law and de Loor–Dobson mixing models gave a reasonable approximation to the measured apparent permittivity for a silty clay loam (34% clay) across the entire water content range. Moreover, the models were able to describe the behavior of apparent permittivity in response to temperature for two soils with contrasting bulk electrical conductivity contributions to losses. These results demonstrate that loss mechanisms and declines in effective frequency need to be considered to accurately predict the soil water content of fine‐textured soils.

Field use and calibration of a TDR-based probe for monitoring water content in a high-clay landslide soil in Austria

Dielectric-based sensors are widely used for field monitoring of soil volumetric water content ( θ v ), including in situ applications in ecological monitoring programs. However, sensor response depends strongly on the location-specific soil properties, which in turn affects measurement accuracy and data processing. Published general or manufacturers' calibrations often misrepresent the θ v -sensor output relationship, requiring soil-specific calibration. We report on use of the CS615 Water Content Reflectometer (WCR) to monitor the soil water dynamics in a creeping flow at a landslide site (Bad Goisern, Austria), and on the soil-specific adjustment of measurement errors. Extraordinary soil conditions (high clay and water contents) caused anomalous overestimation of θ v via the manufacturer's standard calibration. Further, a laboratory calibration had to be aborted due to the intractable soil material. However an in situ field calibration and an ex situ field-soil calibration successfully provided relations between θ v and the probe output (multivibrator period, τ). The calibration was performed as a two-stage procedure according to the inverse regression method. Linear (LR) and multiple (MR) regression models and polynomial (P2, P3) relations were generated via regression analyses. Bias, mean squared error (MSE) and mean deviation (MD) were used to evaluate the quality of θ v estimation using the inverse prediction function. LR and MR models provided better data adjustment than polynomial functions. Best results were derived from MR models including as additional variables temperature ( T) and porosity ( P), and subset-specific ( S) to sensor position in the field (model MR TP S). Measurement error was reduced from 0.068 ± 0.122 m 3 m − 3 (MSE ± σ for the standard calibration) to 0.001 ±0.002 m 3 m − 3 (MSE ± σ for the MR TP S model). Restricted sample size and moisture range impaired the statistical analyses of both field soil calibrations. Deviations of sensor response specific to soil layer and sensor position were observed and statistically confirmed. However, reasonable location-specific calibration functions were obtained for both the entire water content range and the site-specific high moisture range. Our results indicate an especially anomalous, soil pH-dependent response of the WCR (which operates in the lower frequency range 15 to 45 MHz) in a smectite-dominated soil, partly consistent with the findings of Ishida and Makino (1999) for the dielectric behaviour of montmorillonite suspensions. Unfavourable soil conditions, especially high moisture levels combined with high clay contents, demonstrated the limits of WCR-application. Our findings strongly support media-specific sensor calibration over general calibrations, especially for soils with extraordinary and challenging properties.

Heat Effects of Dehydration of Human Serum Albumin in Hydrophilic Organic Solvents

AbstractA thermochemical model for describing the transfer of water from the protein phase to the organic solvent liquid phase and for determining how the solvation ability of organic solvents affects this process was developed. Enthalpy changes on the interaction of dried and hydrated human serum albumin (HSA) with hydrophilic organic solvents (dimethyl sulfoxide, formamide, ethanol, methanol and acetic acid) and water were measured by isothermal calorimetry at 25 °C. The initial hydration level of human serum albumin was varied in the entire water content range from 0–30 % [g water/g HSA]. The dependence of the interaction enthalpies on the initial water content is complex. The interaction enthalpies of the dried HSA with organic solvents are exothermic. At low water contents (less than 0.1 g/g), there is a sharp increase in the interaction enthalpy values. At the highest water contents (more than 0.2 g/g), the interaction enthalpies are endothermic for acetic acid and formamide and exothermic for DMSO, methanol, and ethanol. These thermochemical data were analyzed in conjunction with the results for the water adsorption in organic solvents to calculate the molar enthalpies of dehydration of HSA in organic liquids. It was found that the dehydration enthalpy changes may be endothermic or exothermic depending on the initial water content and the water solvation enthalpy value. From the results obtained, it can be concluded that: (i) only the solvation of water by hydrophilic organic solvent determines the changes in the dehydration enthalpy values, and (ii) the data for the enthalpies of solvation of water by the solvent at infinite dilution reflect this effect.

Evaluation of Methodologies Used for Establishing Soil-Water Characteristic Curve

Abstract Different methodologies have been developed for establishing the soil-water characteristic curve, SWCC. These methodologies employ measurement of the soil suction with the help of different instrumentation techniques. However, as the instruments used for measuring soil suction work efficiently only for a certain range of suction, obtained SWCCs may not be representative. This calls for a systematic investigation, which would be of great help in determining the efficiency of each of these instruments for measuring the soil suction, and hence establishing the SWCC precisely. With this in view, the results obtained from a pressure membrane extractor (PME) and a dewpoint potentiameter (WP4), which are used quite frequently for the said purpose, were evaluated for the soils of entirely different characteristics. This technical note highlights the importance of utilization of the instruments in tandem for conducting multiple suction measurements in order to obtain a representative SWCC that covers the entire range of water content and corresponding suction.