Heating effects on water repellency in Australian eucalypt forest soils and their value in estimating wildfire soil temperatures

Wildfires can induce or enhance soil water repellency under a range of vegetation communities. According to mainly USA-based laboratory studies, repellency is eliminated at a maximum soil temperature (T) of 280–400°C. Knowledge of T reached during a wildfire is important in evaluating post-fire soil physical properties, fertility and seedbed status. T is, however, notoriously difficult to ascertain retrospectively and often based on indicative observations with a large potential error. Soils under fire-prone Australian eucalypt forests tend to be water repellent when dry or moderately moist even if long unburnt. This study aims to quantify the temperature of water repellency destruction for Australian topsoil material sampled under three sites with contrasting eucalypt cover (Eucalyptus sieberi, E. ovata and E. baxteri). Soil water repellency was present prior to heating in all samples, increased during heating, but was abruptly eliminated at a specific T between 260 and 340°C. Elimination temperature varied somewhat between samples, but was found to be dependent on heating duration, with longest duration resulting in lowest elimination temperature. Results suggest that post-fire water repellency may be used as an aid in hindcasting soil temperature reached during the passage of a fire within repellency-prone environments.

Water repellency, near-saturated infiltration and preferential solute transport in a macroporous clay soil

Little attention has been paid to the possibility that soil water repellency could enhance non-equilibrium water flow and solute transport through macropores present in structured clay soils. In this study, we measured infiltration and solute transport in a clay soil under near-saturated conditions in both the field using tension infiltrometers and in the laboratory on undisturbed soil columns. Measurements were made on adjacent plots under grass and continuous arable cultivation. Steady-state field infiltration rates measured using water and ethanol as the infiltrating fluids demonstrated that the soil macroporosity under grass was better developed, but that much of the structural pore system was inactive due to water repellency. No water repellency was detected on the arable plot disturbed by tillage. Dye tracing showed that the conducting macroporosity was largely comprised of earthworm channels in the grassed plot and inter-aggregate voids resulting from ploughing in the arable plot. Tracer breakthrough curves measured on field-dry soil indicated rapid macropore transport in columns taken from both plots, although the degree of non-equilibrium transport appeared somewhat stronger under grass. This result, which was attributed to water repellency, was also consistent with the larger flow-weighted mean pore size found in the field infiltration experiments. It is concluded that water repellency in undisturbed structured clay soils can have significant effects on the occurrence of non-equilibrium water and solute transport in macropores.

Stereocomplexation and monolayer morphologies of a stereoregular poly(methylmethacrylate) mixture formed at the air/water surface

The stereocomplexation of stereoregular PMMA at the air/water interface was proved by structure determination using reflection-absorption IR and grazing incidence X-ray diffraction. Morphological studies on LB films of i- and s-PMMA blends with different ratios help to disclose the stereocomplexation process of stereoregular PMMA at the air/water interface. It was found that the stereocomplexes exist in particle aggregates randomly dispersed at the air/water interface. In the systems with the i:s ratio deviated from 1:2, the molecules, either i-PMMA or s-PMMA, that do not participate in the stereocomplexation build separate layer surrounding the stereocomplexes. This layer is much thinner than the particle aggregates of the stereocomplexes. If the i-PMMA molecules are rich in this thinner layer, crystallization of i-PMMA takes place, which generates lamellar structure besides the stereocomplexes.

Concepts and dimensionality in modeling unsaturated water flow and solute transport

Many environmental studies require accurate simulation of water and solute fluxes in the unsaturated zone. This paper evaluates one- and multi-dimensional approaches for soil water flow as well as different spreading mechanisms to model solute behavior at different scales. For quantification of soil water fluxes,Richards equation has become the standard. Although current numerical codes show perfect water balances, the calculated soil water fluxes in case of head boundary conditions may depend largely on the method used for spatial averaging of the hydraulic conductivity. Atmospheric boundary conditions, especially in the case of phreatic groundwater levels fluctuating above and below a soil surface, require sophisticated solutions to ensure convergence. Concepts for flow in soils with macro pores and unstable wetting fronts are still in development. One-dimensional flow models are formulated to work with lumped parameters in order to account for the soil heterogeneity and preferential flow. They can be used at temporal and spatial scales that are of interest to water managers and policymakers. Multi-dimensional flow models are hampered by data and computation requirements.Their main strength is detailed analysis of typical multi-dimensional flow problems, including soil heterogeneity and preferential flow. Three physically based solute-transport concepts have been proposed to describe solute spreading during unsaturated flow: The stochastic-convective model (SCM), the convection-dispersion equation (CDE), and the fraction aladvection-dispersion equation (FADE). A less physical concept is the continuous-time random-walk process (CTRW). Of these, the SCM and the CDE are well established, and their strengths and weaknesses are identified. The FADE and the CTRW are more recent,and only a tentative strength weakness opportunity threat (SWOT)analysis can be presented at this time. We discuss the effect of the number of dimensions in a numerical model and the spacing between model nodes on solute spreading and the values of the solute-spreading parameters. In order to meet the increasing complexity of environmental problems, two approaches of model combination are used: Model integration and model coupling. Amain drawback of model integration is the complexity of there sulting code. Model coupling requires a systematic physical domain and model communication analysis. The setup and maintenance of a hydrologic framework for model coupling requires substantial resources, but on the other hand, contributions can be made by many research groups.

Extraction of compounds associated with water repellency in sandy soils of different origin

After an initial evaluation of several solvents, the efficiency of Soxhlet extractions with isopropanol/ammonia (s.g. 0.88) (70 : 30 v : v; 24 h) in extracting compounds associated with water repellency in sandy soils was examined using a range of repellent and wettable control soils (n = 15 and 4) from Australia, Greece, Portugal, The Netherlands, and the UK. Extraction efficiency and the role of the extracts in causing soil water repellency was examined by determining extract mass, sample organic carbon content and water repellency (after drying at 20°C and 105°C) pre- and post-extraction, and amounts of aliphatic C–H removed using DRIFT, and by assessing the ability of extracts to cause repellency in acid-washed sand (AWS).

Key findings are: (i) none of organic carbon content, amount of aliphatic C–H, or amount of material extracted give any significant correlation with repellency for this diverse range of soils; (ii) sample drying at 105°C is not necessarily useful before extraction, but may provide additional information on extraction effectiveness when used after extraction; (iii) the extraction removed repellency completely from 13 of the 15 repellent samples; (iv) extracts from all repellent and wettable control soils were capable of inducing repellency in AWS. The findings suggest that compounds responsible for repellency represent only a fraction of the extract composition and that their presence does not necessarily always cause repellency.

A new modelling approach to simulate preferential flow and transport in water repellent media: parameter sensitivity, and effects on crop growth and solute leaching

A modified version of the popular agrohydrological model SWAP has been used to evaluate modelling of soil water flow and crop growth at field situations in which water repellency causes preferential flow. The parameter sensitivity in such situations has been studied. Three options to model soil water flow within SWAP are described and compared: uniform flow, the classical mobile-immobile concept, and a recent concept accounting for the dynamics of finger development resulting from unstable infiltration. Data collected from a severely water-repellent affected soil located in Australia were used to compare and evaluate the usefulness of the modelling options for the agricultural management of such soils.

The study shows that an assumption of uniform flow in a water-repellent soil profile leads to an underestimation of groundwater recharge and an overestimation of plant transpiration and crop production. The new concept of modelling taking finger dynamics into account provides greater flexibility and can more accurately model the observed effects of preferential flow compared with the classical mobile–immobile concept. The parameter analysis indicates that the most important factor defining the presence and extremity of preferential flow is the critical soil water content.

Comparison of the modelling results with the Australian field data showed that without the use of a preferential flow module, the effects of the clay amendments to the soil were insufficiently reproduced in the dry matter production results. This means that the physical characteristics of the soil alone are not sufficient to explain the measured increase in production on clay amended soils. However, modelling with the module accounting for finger dynamics indicated that the preferential flow in water repellent soils that had not been treated with clay caused water stress for the crops, which would explain the decrease in production.

Investigation of compounds causing water repellency in the rhizosphere of sandy soils from a wide range of locations.

Although soils are generally considered to wet readily, some are actually water repellent at the surface and in the rhizosphere. This phenomenon occurs at low to moderate moisture contents and has been reported from soils under a range of vegetation types and from many regions around the globe. Water repellency in soils can have serious environmental implications including reduced seed germination and plant growth as well as irrigation efficiency, accelerated soil erosion, and enhanced leaching of agrochemicals through preferential flow. it has been proposed that water repellency is caused by the accumulation of hydrophobic organic compounds released as root exudates, microbial byproducts or from decomposing organic matter, which are deposited on mineral or aggregate surfaces, or are present as interstitial matter, Few studies to date have attempted to isolate and characterize these compounds and their structure is therefore only poorly understood, These studies have generally focussed on only a single soil or a small range of samples, have not included non-repellent soils as a control and have not always been able to demonstrate that the substances isolated are indeed responsible for repellency formation.

This study reports on the first part (extraction procedures) of a research programme addressing these gaps in current knowledge by investigating a wide range of severely repellent and wettable ‘control’ samples from different countries, and by including assessments of extraction efficiency and ability of extracts to cause repellency. Analytical methods include DRIFT (Diffuse Reflectance Infrared Fourier Transform Spectroscopy) of soils and IR (Infrared) analysis of extracts.

Key findings are that (i) soil sample heating after extraction is valuable in assessing the effectiveness of the extraction procedure, (ii) Soxhlet extraction using isopropanol/ ammonia (70/30 v/v) was the most effective method in extracting hydrophobic compounds, while leaving the ability of extracted compounds to induce water repellency virtually unaffected, (iii) wettable control soils also contain hydrophobic substances capable of inducing water repellency, (iv) the amount of organic compounds extracted was poorly related to sample repellency, indicating that compounds responsible for repellency may only represent a small fraction of the extract, (v) differences in extraction efficiency between different samples indicate that the compounds responsible may differ generically and/or in terms of their bonding to minerals, and (vi) the combination of repellency assessments with DRIFT on soils and JR on extracts used with internal standards has considerable potential to allow quantification of CH bearing organic matter in the soil, the efficiency of extraction processes for its removal, and its significance in causing water repellency in soils.

Conducting polymers with fibrillar morphology synthesized in a biphasic ionic liquid/water system

The synthesis of poly(pyrrole), poly(terthiophene), and poly(3,4-ethylenedioxythiophene) with unusual fibrillar morphologies has been achieved by chemical polymerization in a biphasic ionic liquid/water system. Use of aqueous gold chloride as the oxidant, with the monomers dissolved in a hydrophobic ionic liquid, allows the polymerization to occur at the ionic liquid/water interface. The resultant conducting polymer fibrils are, on average, 50−100 nm wide and can be thousands of nanometers long. The polymers produced in this ionic liquid system are compared to those synthesized in a biphasic chloroform/water system.

Bubble-solid interactions in water and electrolyte solutions

Surface forces between an air bubble and a flat mica surface immersed in aqueous electrolyte solutions have been investigated using a modified surface force apparatus. An analysis of the deformation of the air bubble with respect to the mutual position of the bubble and the mica surface, the capillary pressure, and the disjoining pressure allows the air-liquid surface electrical potential to be determined. The experiments show that a long-range, double-layer repulsion acts between the mica (which is negatively charged) and an air bubble in water and in various electrolyte solutions at low concentration, thereby indicating that the air bubble surface is negatively charged. However, there is clear evidence that charge regulation occurs at the air-water interface to maintain a constant surface potential, and as a result of this, the charge at this interface changes from negative to positive as the bubble approaches the mica surface. Because of the attraction that arises as a result of the charge reversal, a finite force is required to separate the bubble from the mica, though the mica remains wetted by the aqueous phase. At the low concentrations investigated, the potential on the gas-liquid interface is independent of the electrolyte type within experimental uncertainty.

Rational design of monolayers for improved water evaporation mitigation

Seven chemically designed monolayer compounds were synthesized and investigated with comparison to the properties and water evaporation suppression ability of 1-hexadecanol and 1-octadecanol. Increasing the molecular weight and polarity of the compound headgroup drastically altered the characteristics and performance of the monolayer at the air/water interface. Contrary to the common expectation the monolayer's lifetime on the water surface decreased with increasing number of ethylene oxy moieties, thus optimal performance for water evaporation suppression was achieved when only one ethylene oxy moiety was used. Replacing the hydroxyl headgroup with a methyl group and with multiple ethylene oxy moieties resulted in a loss of suppression capability, while an additional hydroxyl group provided a molecule with limited performance against water evaporation. Theoretical molecular simulation demonstrated that for exceptional performance, a candidate needs to possess a high equilibrium spreading pressure, the ability to sustain a highly ordered monolayer with a stable isotherm curve, and low tilt angle over the full studied range of surface pressures by simultaneously maintaining H-bonding to the water surface and between the monolayer chains.

Molecular mechanism of stabilization of thin films for improved water evaporation protection

All-atom molecular dynamics simulations and experimental characterization have been used to examine the structure and dynamics of novel evaporation-suppressing films where the addition of a water-soluble polymer to an ethylene glycol monooctadecyl ether monolayer leads to improved water evaporation resistance. Simulations and Langmuir trough experiments demonstrate the surface activity of poly(vinyl pyrrolidone) (PVP). Subsequent MD simulations performed on the thin films supported by the PVP sublayer show that, at low surface pressures, the polymer tends to concentrate at the film/water interface. The simulated atomic concentration profiles, hydrogen bonding patterns, and mobility analyses of the water-polymer-monolayer interfaces reveal that the presence of PVP increases the atomic density near the monolayer film, improves the film stability, and reduces the mobility of interfacial waters. These observations explain the molecular basis of the improved efficacy of these monolayer/polymer systems for evaporation protection of water and can be used to guide future development of organic thin films for other applications.

Preformed and sprayable polymeric mulch film to improve agricultural water use efficiency

Plastic mulch films are widely used in agriculture to enhance crop production by suppressing weeds, conserving soil water and increasing soil temperature. The majority of plastic mulch films are however not biodegradable and are typically removed after each growing season. Recovery of these plastics from the soil is difficult and can affect successive crop yields while causing substantive cost to the environment and farmers. Due to increasingly stringent regulations regarding use of non-degradable plastic in agriculture they are likely to be phased out in the near future. In the past 10 years several classes of 'biodegradable' materials have been studied but most of these films are reported to be relatively weak in mechanical properties, not efficiently degradable and cost prohibitive.More recently, researchers have turned their attention to sprayable biodegradable polymer coatings for use on soils due to their easy application and versatility. The ability to mix natural additives, plasticizers and fillers to control and improve the mechanical and biodegradation properties of the core polymeric mulch film has been the driving force behind the development of these next generation sprayable polymeric mulch films.There have been many excellent review articles and papers written about polymeric mulch film, but the developing sprayable polymer systems have not been reviewed to the same extent. This paper focusses on the research progress in the area of biodegradable and sprayable polymer mulch film with emphasis on polymer formulations, properties and application. It also discusses current research to highlight the importance, potential benefits and future challenges in developing a cost effective biodegradable sprayable film for use in production agriculture.

Simulation of oleuropein structural conformation in vacuum, water and triolein-water systems using molecular dynamics

Oleuropein, the main phenolic compound of olive leaves, exhibits a unique blend of biological activities and has been shown to locate itself at the oil-water (O/W) interface. This behavior could influence the physico-chemical properties of dispersed systems such as emulsions. In this work, we study the effect of the microenvironment (vacuum, water, and triolein-water) on the conformational preferences of oleuropein using molecular dynamics (MD) simulations at 300K for at least 30ns. The seven torsions that describe the flexible skeleton of oleuropein were monitored together with the distance between the glucose (Glu) and hydroxytyrosol (Hyd) moieties (dglu-hyd) of the molecule. The obtained trajectories demonstrated that oleuropein adopts different conformations that depend on the environment. The preferential conformers in each system were analyzed for their molecular geometry and internal energy. In vacuum, the oleuropein preferential conformation is tight with the glucose moiety in close proximity with the hydroxytyrosol moiety. In water, oleuropein preferential conformers presented large differences in their structural properties, varying from a close like U form, and a semi-opened form, to an opened form characterized by high fluctuations in dglu-hyd values. In a triolein-water system, oleuropein tends to adopt a more open form where the glucose moiety could be approximately aligned with the hydroxytyrosol and elenolic acid moieties. Based on a calculation at the HF/6-31G* level, these flexibilities of oleuropein required energy of 19.14kcal/mol in order to adopt the conformation between water and triolein-water system. A radial distribution function (RDF) analysis showed that specific hydroxyl groups of Hyd and Glu interact with water molecules, enabling us to understand the amphiphilic character of oleuropein at the triolein-water interface. MD calculations together with interfacial tension measurements revealed that the oleuropein binding at O/W interface is an enthalpy driven mechanism.

Effect of soil texture and wheat plants on N₂O fluxes: a lysimeter study

Agricultural soils are a major source of nitrous oxide (N2O) emissions and an understanding of factors regulating such emissions across contrasting soil types is critical for improved estimation through modelling and mitigation of N2O. In this study we investigated the role of soil texture and its interaction with plants in regulating the N2O fluxes in agricultural systems. A measurement system that combined weighing lysimeters with automated chambers was used to directly compare continuously measured surface N2O fluxes, leaching losses of water and nitrogen and evapotranspiration in three contrasting soils types of the Riverine Plain, NSW, Australia. The soils comprised a deep sand, a loam and a clay loam with and without the presence of wheat plants. All soils were under the same fertilizer management and irrigation was applied according to plant water requirements. In fallow soils, texture significantly affected N2O emissions in the order clay loam > loam > sand. However, when planted, the difference in N2O emissions among the three soils types became less pronounced. Nitrous oxide emissions were 6.2 and 2.4 times higher from fallow clay loam and loam cores, respectively, compared with cores planted with wheat. This is considered to be due to plant uptake of water and nitrogen which resulted in reduced amounts of soil water and available nitrogen, and therefore less favourable soil conditions for denitrification. The effect of plants on N2O emissions was not apparent in the coarse textured sandy soil probably because of aerobic soil conditions, likely caused by low water holding capacity and rapid drainage irrespective of plant presence resulting in reduced denitrification activity. More than 90% of N2O emissions were derived from denitrification in the fine-textured clay loam-determined for a two week period using K15NO3 fertilizer. The proportion of N2O that was not derived from K15NO3 was higher in the coarse-textured sand and loam, which may have been derived from soil N through nitrification or denitrification of mineralized N. Water filled pore space was a poorer predictor of N2O emissions compared with volumetric water content because of variable bulk density among soil types. The data may better inform the calibration of greenhouse gas prediction models as soil texture is one of the primary factors that explain spatial variation in N2O emissions by regulating soil oxygen. Defining the significance of N2O emissions between planted and fallow soils may enable improved yield scaled N2O emission assessment, water and nitrogen scheduling in the pre-watering phase during early crop establishment and within rotations of irrigated arable cropping systems.

Mapping land use in a large agricultural basin : a comparison between classification techniques

In order to facilitate the better management of river basin resources, the Glenelg-Hopkins region in south-east Australia required an accurate and up to date land use map. Land use has a major impact on Australia's natural resources including its soil, water, flora and fauna and plays a major role in determining basin health. Inappropriate land use and practices have contributed to extensive dryland salinity and water quality problems. Land use data is often required for environmental models and in most cases the reliability of model outputs is dependent on the spatial detail and accuracy of the land use mapping. This paper examines methods to obtain an up to date land use map and a detailed accuracy assessment using Landsat ETM+ data for a regional basin. A multi-source based approach allowed the collection of 4817 ground truth data points from the field investigation. This enabled researchers to (i) incorporate a full range of information into digital image analysis with significant improvements in accuracy and (ii) hold sufficient independent references for an accurate error assessment. Classification accuracy was significantly improved using a stratification design, in which the region is sub-divided into smaller homogenous areas as opposed to a full scene classification technique. The overall classification accuracy was 84% (KHAT= 0.833) for the stratified approach compared to 76% (KHAT= 0.743) for the full scene classification. Effective assessment, planning and management of basins are dependent on a sound knowledge of the distribution and variability of land use.