Effect of Different Minerals on Water Stability and Wettability of Soil Silt Aggregates.

Knowledge on the effects of minerals on soil water stability and wettability is mostly gained from experiments on natural soils of different mineral composition. To gain a "clearer" picture, the water stability and wettability of artificial aggregates composed of soil silt and various proportions of pure minerals: kaolinite, montmorillonite, illite, zeolite and goethite, were examined. The wettability was attributed to contact angles measured goniometrically and to the water drop penetration time (WDPT). The water stability was measured by monitoring of air bubbling after aggregate immersion in water and the shrinking sphere model was used to analyse aggregates' destruction kinetics. The rate of aggregate destruction in water increased with increasing mineral content and it slightly decreased for aggregates composed of all pure minerals except goethite. An apparent hydrophobicity period (a period where the bubbling stopped for some time), resulted most probably from the wavy shape of pores, was observed mainly for aggregates with low mineral proportions. Among all studied minerals, kaolinite increased the water contact angle and water repellency to the greatest extent. With increasing the mineral content in the aggregates up to 8%, contact angles decreased and then increased. Contact angles did not correlate with aggregates' stability. Aggregates more rapidly penetrated by water (shorter WDPT) were destroyed faster. Water stability of aggregates containing all minerals except illite appeared to be higher for the more mechanically resistant aggregates.

Impact of Chitosan on the Mechanical Stability of Soils.

Chitosan is becoming increasingly applied in agriculture, mostly as a powder, however little is known about its effect on soil mechanical properties. Uniaxial compression test was performed for cylindrical soil aggregates prepared from four soils of various properties (very acidic Podzol, acidic Arenosol, neutral Fluvisol and alkaline Umbrisol) containing different proportions of two kinds of chitosan (CS1 of higher molecular mass and lower deacetylation degree, and CS2 of lower molecular mass and higher deacetylation degree), pretreated with 1 and 10 wetting-drying cycles. In most cases increasing chitosan rates successively decreased the mechanical stability of soils that was accompanied by a tendential increase in soil porosity. In one case (Fluvisol treated with CS2) the porosity decreased and mechanical stability increased with increasing chitosan dose. The behavior of acidic soils (Podzol and Arenosol) treated with CS2, differed from the other soils: after an initial decrease, the strength of aggregates increased with increasing chitosan amendment, despite the porosity consequently decreasing. After 10 wetting-drying cycles, the strength of the aggregates of acidic soils appeared to increase while it decreased for neutral and alkaline soils. Possible mechanisms of soil-chitosan interactions affecting mechanical strength are discussed and linked with soil water stability and wettability.

Impact of Chitosan on Water Stability and Wettability of Soils.

Chitosan has become increasingly applied in agriculture worldwide, thus entering the soil environment. We hypothesized that chitosan should affect the water stability of soil. Since this problem has not been studied to date, we examined, for the first time, the influence of chitosan on the water stability and wettability of soil aggregates. The aggregates were prepared from four soils with various properties amended with different amounts of two kinds of powdered chitosan, and subjected to 1 and/or 10 wetting-drying cycles. The water stability was measured by monitoring air bubbling after aggregate immersion in water, and the wettability was measured by a water drop penetration test. The biopolymer with a lower molecular mass, lower viscosity, and higher degree of deacetylation was more effective in increasing the water stability of the soil than the biopolymer with a higher molecular mass, higher viscosity, and lower deacetylation degree. After a single wetting-drying cycle, the water stability of the soil aggregates containing chitosan with a higher molecular mass was generally lower than that of the soil; after ten wetting-drying cycles, the water stability increased 1.5 to 20 times depending on the soil. The addition of low-molecular-mass chitosan after a single wetting-drying cycle caused the water stability to become one to two hundred times higher than that of the soil. A trial to find out which soil properties (pH, C and N content, bulk density, porosity, and particle size distribution) are responsible for the effectiveness of chitosan action was not successful, and this will be the objective of further studies.

Structure and Strength of Artificial Soils Containing Monomineral Clay Fractions.

Structure and strength are responsible for soil physical properties. This paper determines in a uniaxial compression test the strength of artificial soils containing different proportions of various clay-size minerals (cementing agents) and silt-size feldspar/quartz (skeletal particles). A novel empirical model relating the maximum stress and the Young's modulus to the mineral content basing on the Langmuir-type curve was proposed. By using mercury intrusion porosimetry (MIP), bulk density (BD), and scanning electron microscopy (SEM), structural parameters influencing the strength of the soils were estimated and related to mechanical parameters. Size and shape of particles are considered as primary factors responsible for soil strength. In our experiments, the soil strength depended primarily on the location of fine particles in respect to silt grains and then, on a mineral particle size. The surface fractal dimension of mineral particles played a role of a shape parameter governing soil strength. Soils containing minerals of higher surface fractal dimensions (rougher surfaces) were more mechanically resistant. The two latter findings appear to be recognized herein for the first time.

Breakage Strength of Wood Sawdust Pellets: Measurements and Modelling.

Wood pellets are an important source of renewable energy. Their mechanical strength is a crucial property. In this study, the tensile strength of pellets made from oak, pine, and birch sawdust with moisture contents of 8% and 20% compacted at 60 and 120 MPa was determined in a diametral compression test. The highest tensile strength was noted for oak and the lowest for birch pellets. For all materials, the tensile strength was the highest for a moisture content of 8% and 120 MPa. All pellets exhibited a ductile breakage mode characterised by a smooth and round stress-deformation relationship without any sudden drops. Discrete element method (DEM) simulations were performed to check for the possibility of numerical reproduction of pelletisation of the sawdust and then of the pellet deformation in the diametral compression test. The pellet breakage process was successfully simulated using the DEM implemented with the bonded particle model. The simulations reproduced the results of laboratory testing well and provided deeper insight into particle-particle bonding mechanisms. Cracks were initiated close to the centre of the pellet and, as the deformation progressed, they further developed in the direction of loading.

Effect of Low Zeolite Doses on Plants and Soil Physicochemical Properties.

Thousands of tons of zeolitic materials are used yearly as soil conditioners and components of slow-release fertilizers. A positive influence of application of zeolites on plant growth has been frequently observed. Because zeolites have extremely large cation exchange capacity, surface area, porosity and water holding capacity, a paradigm has aroused that increasing plant growth is caused by a long-lasting improvement of soil physicochemical properties by zeolites. In the first year of our field experiment performed on a poor soil with zeolite rates from 1 to 8 t/ha and N fertilization, an increase in spring wheat yield was observed. Any effect on soil cation exchange capacity (CEC), surface area (S), pH-dependent surface charge (Qv), mesoporosity, water holding capacity and plant available water (PAW) was noted. This positive effect of zeolite on plants could be due to extra nutrients supplied by the mineral (primarily potassium-1 ton of the studied zeolite contained around 15 kg of exchangeable potassium). In the second year of the experiment (NPK treatment on previously zeolitized soil), the zeolite presence did not impact plant yield. No long-term effect of the zeolite on plants was observed in the third year after soil zeolitization, when, as in the first year, only N fertilization was applied. That there were no significant changes in the above-mentioned physicochemical properties of the field soil after the addition of zeolite was most likely due to high dilution of the mineral in the soil (8 t/ha zeolite is only ~0.35% of the soil mass in the root zone). To determine how much zeolite is needed to improve soil physicochemical properties, much higher zeolite rates than those applied in the field were studied in the laboratory. The latter studies showed that CEC and S increased proportionally to the zeolite percentage in the soil. The Qv of the zeolite was lower than that of the soil, so a decrease in soil variable charge was observed due to zeolite addition. Surprisingly, a slight increase in PAW, even at the largest zeolite dose (from 9.5% for the control soil to 13% for a mixture of 40 g zeolite and 100 g soil), was observed. It resulted from small alterations of the soil macrostructure: although the input of small zeolite pores was seen in pore size distributions, the larger pores responsible for the storage of PAW were almost not affected by the zeolite addition.

Arsenate Adsorption on Fly Ash, Chitosan and Their Composites and Its Relations with Surface, Charge and Pore Properties of the Sorbents.

One of the ways to recycle millions of tons of fly ash and chitin wastes produced yearly is their utilization as low-cost sorbents, mainly for heavy metal cations and organic substances. To improve their sorption efficiency, fly ashes have been thermally activated or modified by chitosan. We aimed to deeply characterize the physicochemical properties of such sorbents to reveal the usefulness of modification procedures and their effect on As(V) adsorption. Using low temperature nitrogen adsorption, scanning electron microscopy, mercury intrusion porosimetry, potentiometric titration and adsorption isotherms of As(V) anions, surface, pore, charge and anion adsorption parameters of fly ash activated at various temperatures, chitosan, and fly ash modified by chitosan were determined. Arsenate adsorption equilibrium (Langmuir model), kinetics (pseudo-second order model) and thermodynamics on the obtained materials were studied. Neither temperature activation nor chitosan modifications of fly ash were necessary and profitable for improving physicochemical properties and As(V) adsorption efficiency of fly ash. Practically, the physicochemical parameters of the sorbents were not related to their anion adsorption parameters.

Fluorapatite ceramics for bone tissue regeneration: Synthesis, characterization and assessment of biomedical potential.

Calcium phosphates, due to their similarity to the inorganic fraction of mineralized tissues, are of great importance in treatment of bone defects. In order to improve the biological activity of hydroxyapatite (HAP), its fluoride-substituted modification (FAP) was synthesized using the sol-gel method and calcined at three different temperatures in the range of 800-1200 °C. Physicochemical and biological properties were evaluated to indicate which material would support bone regeneration the best. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectrometry (EDS), and Fourier transform infrared spectroscopy (FTIR) revealed that fluoride ions were incorporated into the apatite lattice structure. In studies it was found that fluorapatite sintered at the highest temperature had the lowest porosity, no internal pores and the highest density. In vitro ion reactivity assessments showed that during the 28-day immersion of the samples in the simulated body fluid, the uptake of calcium and phosphorus ions was inversely correlated to the calcination temperature. All tested materials were non-toxic since the cytotoxicity MTT assay demonstrated that the viability of preosteoblast cells incubated with sample extracts was high. Fluorapatite sintered at 800 °C was determined to be of optimal porosity and fluoride release capacity and then used in cell proliferation studies. The results showed that it significantly shortened the doubling time and thus enhanced the proliferation of osteogenic cells, as compared to the fluoride solutions and control group. Therefore, this material is proposed for the use in orthopedic applications and bone tissue engineering.

Environmental-Friendly Modifications of Zeolite to Increase Its Sorption and Anion Exchange Properties, Physicochemical Studies of the Modified Materials.

Zeolites, naturally possessing a high negative surface charge and large specific surface, are used in agriculture as cationic fertilizers, water holders, heavy metals, and organic pollutants sorbents. Since some nutrients occur in anionic forms, there is a need to modify the zeolite surface to hold anions. In this study, hydrogen (hydrochloric acid), iron (Fe2+ and Fe3+), and aluminum cations as well as the influence of sodium hydroxide modifiers on the specific surface area, water vapor, adsorption energy, fractal dimension, mesopore volumes and radii, electrokinetic (zeta) potential, and isoelectric point were investigated. The use of alkali solution did not affect the zeolite properties significantly, whereas hydrogen, iron, and treatments with aluminum cations resulted in an increase in the specific surface area, mesopore volumes, and radii, and a decrease in the water-binding forces. Aluminum cations were the most effective in recharging the zeolite surface from negative to positive, shifting the isoelectric point toward the highest values. Calcination enlarged the negative surface charge and mesopore radius, and diminished the surface area and mesopore volume. The modified zeolites are promising carriers of anionic nutrients, large surface area sorbents, and suppliers of water for plant roots in soil.

Evaluation of Hydrocarbon Soil Pollution Using E-Nose.

The possibility of detecting low levels of soil pollution by petroleum fuel using an electronic nose (e-nose) was studied. An attempt to distinguish between pollution caused by petrol and diesel oil, and its relation to the time elapsed since the pollution event was simultaneously performed. Ten arable soils, belonging to various soil groups from the World Reference Base (WRB), were investigated. The measurements were performed on soils that were moistened to field capacity, polluted separately with both hydrocarbons, and then allowed to dry slowly over a period of 180 days. The volatile fingerprints differed throughout the course of the experiment, and, by its end, they were similar to those of the unpolluted soils. Principal component analysis (PCA) and artificial neural network (ANN) analysis showed that the e-nose results could be used to detect soil contamination and distinguish between pollutants and contamination levels.

Microstructural Differences in Response of Thermoresistant (Ceramic) and Standard (Granite) Concretes on Heating. Studies Using SEM and Nonstandard Approaches to Microtomography and Mercury Intrusion Porosimetry Data.

The microstructure of concretes containing ceramic sanitary ware waste and granite aggregates was studied using scanning electron microscopy, mercury intrusion porosimetry and computer microtomography, before and after cyclic heating of the concretes to 1000 °C. All methods showed an increase in porosities in the concretes after heating. The proposed new approach to microtomography data analysis detected a much higher increase in the number of cracks in granite than in ceramic concrete after heating. This new approach to combining mercury intrusion and microtomography data showed that heating led to the narrowing of throats connecting smaller pore voids and a broadening of throats connecting larger pore voids, in both concretes.

Evaluating Soil Moisture Status Using an e-Nose.

The possibility of distinguishing different soil moisture levels by electronic nose (e-nose) was studied. Ten arable soils of various types were investigated. The measurements were performed for air-dry (AD) soils stored for one year, then moistened to field water capacity and finally dried within a period of 180 days. The volatile fingerprints changed during the course of drying. At the end of the drying cycle, the fingerprints were similar to those of the initial AD soils. Principal component analysis (PCA) and artificial neural network (ANN) analysis showed that e-nose results can be used to distinguish soil moisture. It was also shown that different soils can give different e-nose signals at the same moistures.

Modification of Lightweight Aggregates' Microstructure by Used Motor Oil Addition.

An admixture of lightweight aggregate substrates (beidellitic clay containing 10 wt % of natural clinoptilolite or Na-P1 zeolite) with used motor oil (1 wt %-8 wt %) caused marked changes in the aggregates' microstructure, measured by a combination of mercury porosimetry (MIP), microtomography (MT), and scanning electron microscopy. Maximum porosity was produced at low (1%-2%) oil concentrations and it dropped at higher concentrations, opposite to the aggregates' bulk density. Average pore radii, measured by MIP, decreased with an increasing oil concentration, whereas larger (MT) pore sizes tended to increase. Fractal dimension, derived from MIP data, changed similarly to the MIP pore radius, while that derived from MT remained unaltered. Solid phase density, measured by helium pycnometry, initially dropped slightly and then increased with the amount of oil added, which was most probably connected to changes in the formation of extremely small closed pores that were not available for He atoms.

Effect of randomly methylated beta-cyclodextrin on physical properties of soils.

The application of cyclodextrins in several soil remediation technologies has been increasingly studied, but little is known about their effects on soil physical properties. One of the popular soil remediation additives, randomly methylated beta-cyclodextrin (RAMEB), was found to significantly alter surface and pore properties of soil clay minerals. Therefore, in this paper we studied the effect of various RAMEB doses on physical properties of selected soils, representing a wide range of clay content (3-49%). The results showed that soil physical properties were greatly modified by RAMEB treatment. Analysis of water vapor adsorption isotherms revealed that RAMEB increased water adsorption and surface area in sandy soils and decreased them in clayey soils. An increase in adsorption energy of water in RAMEB-treated soils indicated that desorption of nonpolar pollutants can be enhanced. Water vapor desorption isotherms showed that the volumes and radii of micropores (nanometers range) increased above 1% RAMEB concentration. The micropores became more rough and complex after RAMEB treatment as deduced from an increase in fractal dimensions. The volume of soil mesopores measured by mercury intrusion porosimetry (micrometers range) gradually decreased in most soils with an increase in RAMEB concentration whereas the average mesopore radius increased, indicating that finer mesopores were blocked by RAMEB. Measurements of the granulometric composition of soils by sedimentation analysis showed that the amount of coarse-size soil fractions increased on the expense of finer fractions due to aggregation of smaller particles. Behavior of the studied soils after RAMEB treatment depended on their clay content and the dose of cyclodextrin. In clay-rich soils, strong interactions of cyclodextrins with the soil solid phase governed the resulting soil properties. In clay-poor soils, the cyclodextrin excess (not interacted with clays) played a dominant role. Modification of surface, pore, and aggregation properties of soils by RAMEB can have a significant effect in soil remediation technologies.