Functional Hydrogels for Agricultural Application.

Ten different hydrogels were prepared and analyzed from the point of view of their use in soil. FT-IR spectra, morphology, swelling ability, and rheological properties were determined for their characterization and appraisal of their stability. The aim was to characterize prepared materials containing different amounts of NPK as mineral fertilizer, lignohumate as a source of organic carbon, and its combination. This study of stability was focused on utility properties in their application in soil-repeated drying/re-swelling cycles and possible freezing in winter. Lignohumate supported the water absorbency, while the addition of NPK caused a negative effect. Pore sizes decreased with NPK addition. Lignohumate incorporated into polymers resulted in a much miscellaneous structure, rich in different pores and voids of with a wide range of sizes. NPK fertilizer supported the elastic character of prepared materials, while the addition of lignohumate shifted their rheological behavior to more liquid. Both dynamic moduli decreased in time. The most stable samples appeared to contain only one fertilizer constituent (NPK or lignohumate). Repeated re-swelling resulted in an increase in elastic character, which was connected with the gradual release of fertilizers. A similar effect was observed with samples that were frozen and defrosted, except samples containing a higher amount of NPK without lignohumate. A positive effect of acrylamide on superabsorbent properties was not confirmed.

Effect of Chitosan as Active Bio-colloidal Constituent on the Diffusion of Dyes in Agarose Hydrogel.

Agarose hydrogel was enriched by chitosan as an active substance for the interactions with dyes. Direct blue 1, Sirius red F3B, and Reactive blue 49 were chosen as representative dyes for the study of the effect of their interaction with chitosan on their diffusion in hydrogel. Effective diffusion coefficients were determined and compared with the value obtained for pure agarose hydrogel. Simultaneously, sorption experiments were realized. The sorption ability of enriched hydrogel was several times higher in comparison with pure agarose hydrogel. Determined diffusion coefficients decreased with the addition of chitosan. Their values included the effects of hydrogel pore structure and interactions between chitosan and dyes. Diffusion experiments were realized at pH 3, 7, and 11. The effect of pH on the diffusivity of dyes in pure agarose hydrogel was negligible. Effective diffusion coefficients obtained for hydrogels enriched by chitosan increased gradually with increasing pH value. Electrostatic interactions between amino group of chitosan and sulfonic group of dyes resulted in the formation of zones with a sharp boundary between coloured and transparent hydrogel (mainly at lower pH values). A concentration jump was observed at a given distance from the interface between hydrogel and the donor dye solution.

How the Addition of Chitosan Affects the Transport and Rheological Properties of Agarose Hydrogels.

Agarose hydrogels enriched by chitosan were studied from a point of view diffusion and the immobilization of metal ions. Copper was used as a model metal with a high affinity to chitosan. The influence of interactions between copper and chitosan on transport properties was investigated. Effective diffusion coefficients were determined and compared with values obtained from pure agarose hydrogel. Their values increased with the amount of chitosan added to agarose hydrogel and the lowest addition caused the decrease in diffusivity in comparison with hydrogel without chitosan. Liesegang patterns were observed in the hydrogels with higher contents of chitosan. The patterns were more distinct if the chitosan content increased. The formation of Liesegang patterns caused a local decrease in the concentration of copper ions and concentration profiles were affected by this phenomenon. Thus, the values of effective diffusion coefficient covered the influences of pore structure of hydrogels and the interactions between chitosan and metal ions, including precipitation on observed Liesegang rings. From the point of view of rheology, the addition of chitosan resulted in changes in storage and loss moduli, which can show on a "more liquid" character of enriched hydrogels. It can contribute to the increase in the effective diffusion coefficients for hydrogels with higher content of chitosan.

Diffusion of dyes in polyelectrolyte-surfactant hydrogels.

In this work, hydrogels formed by interaction of biopolymeric electrolytes and oppositely charged surfactants are studied from the point of view of their ability to incorporate model hydrophobic dyes in their micelle-like structure. Two types of hydrogels were investigated. The first type was based on cationized dextran cross-linked by sodium dodecylsulphate. The second type was prepared by interactions of hyaluronan with carbethoxypendecinium bromide (septonex). Nile red and Atto488 were used as model dyes for the diffusion experiments. The dyes were dissolved in two different media: surfactant and physiological saline. The diffusion of dyes into hydrogel was monitored over time. Effective diffusion coefficients were determined. It was found that their values are strongly influenced by the hydrogel character, the types of dye used and the solvent. The obtained effective coefficients were higher in comparison with the values determined for the diffusion in the opposite direction (release from the hydrogel). The dyes are presented as free in physiological saline and in the form of micelles or micelle aggregates in surfactants. During diffusion into the hydrogel, they can be gradually incorporated in a "pearl necklace structure" which suppresses their mobility. In contrast, this partial immobilization of dyes can increase the concentration gradient which is a driving force of diffusion. Also, the gradual incorporation of dyes into hydrogel structures influences the values of the effective diffusion coefficients.

The Effect of Supramolecular Humic Acids on the Diffusivity of Metal Ions in Agarose Hydrogel.

Humic acids are known as natural substances of a supramolecular nature. Their self-assembly ability can affect the migration of heavy metals and other pollutants in nature. The formation of metal-humic complexes can decrease their mobility and bioavailability. This study focuses on metal ions diffusion and immobilization in humic hydrogels. Humic acids were purchased from International Humic Substances Society (isolated from different matrices-peat, soil, leonardite, water) and extracted from lignite mined in Czech Republic. Copper(II) ions were chosen as a model example of reactive metals for the diffusion experiments. The model of instantaneous planar source was used for experimental data obtained from monitoring the time development of copper(II) ions distribution in hydrogel. The effective diffusion coefficients of copper(II) ions showed the significant dependence on reaction ability of humic hydrogels. Lower amounts of the acidic functional groups caused an increase in the effective diffusion coefficient. In general, diffusion experiments seem to act as a valuable method for reactivity mapping studies on humic substances.

Mean Activity Coefficients of Humic Acids as Physicochemical Characteristics of Their Behavior in Water Environment.

In this work, the dissociation of humic acids is investigated from the point of view of their mean activity coefficients. They are determined on the basis of two different concepts: sparingly soluble substance and multistep mechanism. It was found that the mean activity coefficients are generally higher, if the traditional concept is applied to the data, excepting the HA-A sample. Both the used concepts provide the mean activity coefficients dependent on the ionic strength, the amount of dissolved humic acids, and the types of electrolyte added in the studied suspensions. Their values based on the concept of a multistep mechanism and determined for humic acids in NaCl and NaI form a continuous curve and the individual character of their ions did not assert. It means that activity coefficients were affected only by the ionic strength and valence factor of the electrolytes irrespective of their chemical composition. The mean activity coefficients obtained for humic acids in HCl are lower in comparison with NaCl and NaI due to the common ion H+. Comparing the results obtained for individual humic acids, we can state that the results obtained for the HA-E sample are very different from those of other samples. It seems that its solubility is very high, but the majority of the dissolved particles remained in the molecular form and only a small amount of ions is formed.

How the Supramolecular Nature of Lignohumate Affects Its Diffusion in Agarose Hydrogel.

Lignohumate, as an industrially produced analog of natural humic substances, is studied from the point of view of its diffusion properties. This work focuses on its permeation ability, important in agricultural and horticultural applications, connected with its penetration into plant organs as leaves and roots. The hydrogel based on agarose was used as a model material for the diffusion of lignohumate. Two types of experiments were realized: the diffusion of lignohumate in the hydrogel diffusion couple and the diffusion of lignohumate from its solution into hydrogel. The diffusion coefficient of lignohumate in the hydrogel was determined and used for the modelling of the time development of concentration profiles. It was found that the model agrees with experimental data for short times but an accumulation of lignohumate in front of the interface between donor and acceptor hydrogels was observed after several days. The particle size distribution of lignohumate and changes in the E4/E6 ratio used as an indicator of molecular weight of humic substances were determined. The results showed that the supramolecular structure of lignohumate can react sensitively to actual changes in its environs and thus affect their mobility and permeability into different materials. A filtration effect at the interface can be observed as an accompanying phenomenon of the re-arrangement in the lignohumate secondary structure.

Agarose Hydrogels Enriched by Humic Acids as the Complexation Agent.

The transport properties of agarose hydrogels enriched by humic acids were studied. Methylene blue, rhodamine 6G and Cu(II) ions were incorporated into hydrogel as diffusion probes, and then their release into water was monitored. Cu(II) ions as well as both the dyes studied in this work have high affinity to humic substances and their interactions strongly affected their diffusion in hydrogels. It was confirmed that humic acids retarded the transport of diffusion probes. Humic acids' enrichment caused the decrease in the values of effective diffusion coefficients due to their complexation with diffusion probes. In general, the diffusion of dyes was more affected by the complexation with humic acids in comparison with Cu(II) ions. The effect of complexation was selective for the particular diffusion probe. The strongest effect was obtained for the diffusion of methylene blue. It was assumed that metal ions interacted preferentially with acidic functional groups. In contrast to Cu(II) ions, dyes can interact with acidic functional groups, and the condensed cyclic structures of the dye probes supported their interactions with the hydrophobic domains of humic substances.

Characterization of humic acids in a continuous-feeding vermicomposting system with horse manure.

The increasing numbers of kept horses create problems with processing horse manure as important local waste. This work was focused on horse manure vermicomposting in a real-field continuous-feeding system under controlled conditions, and on the complex study of the maturity and stability of the produced vermicompost. Commonly used simple indicators such as the C/N ratio, N-NH4+/N-NO3- ratio, DOC or ion exchange capacity, and also more advanced spectroscopic and thermoanalytic techniques were used and applied on the humic substances isolated from the vermicompost during its maturation (12 months in total). When compared with the original horse manure, vermicomposting decreased the aliphatic, protein-like, and polysaccharide humic components, whereas vermicomposting increased the aromaticity and contents of oxygen-containing functional groups. The typical tryptophan-like fluorophores in the manure, corresponding to the freshly produced organic matter of biological or microbial origin, were progressively transformed to humic-like fluorophores during vermicomposting. The most thermally labile humic fraction disappeared quickly during the very early vermicomposting stages. The results of spectroscopic and thermogravimetric analyses suggest that stable and mature vermicompost was produced after 6-9 months of vermicomposting, which was also supported by biologically-based maturity indicators.

A simple technique for assessing the cuticular diffusion of humic acid biostimulants.

BACKGROUND: Experimental determination of the extent and rate of transport of liquid humates supplied to plants is critical in testing physiological effects of such biostimulants which are often supplied as foliar sprays. Therefore, an original experimental method for the qualitative investigation and quantitative description of the penetration of humates through plant cuticles is proposed, tested, and evaluated. RESULTS: The proposed method involves the isolation of model plant leaf cuticles and the subsequent in vitro evaluation of cuticular humate transport. The employed novel methodology is based on a simple diffusion couple arrangement involving continuous spectrophotometric determination of the amount of penetrated humate in a hydrogel diffusion medium. Prunus laurocerasus leaf cuticles were isolated by chemical and enzymatic treatment and the rate of cuticular penetration of a commercial humate (lignohumate) was estimated over time in quantitative and qualitative terms. Different rates of lignohumate transport were determined for abaxial and adaxial leaf cuticles also in relation to the different cuticular extraction methods tested. CONCLUSIONS: The proposed methodology represents a simple and cheap experimental tool for the study on the trans-cuticular penetration of humic-based biostimulants.

How Humic Acids Affect the Rheological and Transport Properties of Hydrogels.

Humic acids are often regarded as substances with a supramolecular structure which plays an important role in Nature. Their addition into hydrogels can affect their behavior and functioning in different applications. This work is focused on the properties of widely-used hydrogel based on agarose after addition of humic acids-the protonated H-form of humic acids and humic acids with methylated carboxylic groups. Hydrogels enriched by humic acids were studied in terms of their viscoelastic and transport properties. Rotational rheometry and methods employing diffusion cells were used in order to describe the influence of humic acids on the properties and behavior of hydrogels. From the point of view of rheology the addition of humic acids mainly affected the loss modulus corresponding to the relaxation of hydrogel connected with its flow. In the case of diffusion experiments, the transport of dyes (methylene blue and rhodamine) and metal ions (copper and nickel) through the hydrogel was affected by interactions between humic acids and the diffusion probes. The time lag in the hydrogel enriched by humic acids was prolonged for copper, methylene blue and rhodamine. In contrast, the presence of humic acids in hydrogel slightly increased the mobility of nickel. The strongest influence of the methylation of humic acids on diffusion was observed for methylene blue.

Size and Charge Evaluation of Standard Humic and Fulvic Acids as Crucial Factors to Determine Their Environmental Behavior and Impact.

In this work, the size and charge of humic and fulvic standards purchased from the International Humic Substances Society are presented and discussed. The secondary structure of humic substances in water environment as well as the size and shape of the dissolved humic species and their changes are ill-defined, very dynamic and can be strongly affected by environmental conditions as the concentration, pH, and ionic strength. They have a strong propensity to aggregate which control their interactions with other components, mobility, and functioning in the environment. Particle size distributions were determined by means of dynamic light scattering, zeta potential by Doppler electrophoresis. The intensity, volume, and number particle size distribution were obtained. Two or three different size fractions were detected in the studied systems. Large macroparticles (>1 µm) were observed in the majority of them, mainly in the case of more concentrated solutions. Medium fractions of fulvic submicroparticles had higher average diameters (500-1,200 nm) than those in humic acids (300-600 nm). Small nanoparticles (<100 nm) were detected mainly in alkaline solutions. Fulvic acids with more functional groups (active sites) can form more easily bigger particles mainly in medium concentration region. Alkaline conditions supported the expansion of humic and fulvic coils and liberation of small particles from them. The colloidal stability, indicated by more negative zeta potentials, was higher for humic acids. In the case of fulvic acids, the colloidal stability increased with increasing pH as a result of the dissociation of their functional groups. The increase of particle size corresponded usually with higher stability.

Transport of Organic Compounds Through Porous Systems Containing Humic Acids.

Soil pollution by the presence of different contaminants (e.g. heavy metal ions or pesticides) is one of the biggest problems worldwide. The positive affinity of natural humic acids towards these contaminants might contribute to the soil and ground water protection; therefore it is necessary to study the reactivity and barrier properties of humic acids. An original reactivity-mapping tool based on diffusion techniques designed to study the reactivity and barrier properties of polyelectrolytes was developed and tested on humic acids. The results of diffusion experiments demonstrate that the electrostatic interactions between humic acids functioning as a polyelectrolyte interpenetrated in a supporting hydrogel matrix (agarose) and cationic dye (methylene blue) as a model solute have a crucial impact on the rate of diffusion processes and on the barrier properties of hydrogels. The intensity of interactions was evaluated by fundamental diffusion parameters (effective diffusion coefficients and breakthrough time). The impact of modification of humic acids was also studied by means of diffusion experiments conducted on two types of standard humic acids (Leonardite 1S104H) and humic acids with selectively methylated carboxylic groups.

The Role of Concentration and Solvent Character in the Molecular Organization of Humic Acids.

The molecular organization of humic acids in different aqueous solutions was studied over a wide concentration range (0.01-10 g·dm-3). Solutions of humic acids were prepared in three different media: NaOH, NaCl, and NaOH neutralized by HCl after dissolution of the humic sample. Potentiometry, conductometry, densitometry, and high resolution ultrasound spectrometry were used in order to investigate conformational changes in the humic systems. The molecular organization of humic acids in the studied systems could be divided into three concentration ranges. The rearrangements were observed at concentrations of ~0.02 g·dm-3 and ~1 g·dm-3. The first "switch-over point" was connected with changes in the hydration shells of humic particles resulting in changes in their elasticity. The compressibility of water in the hydration shells is less than the compressibility of bulk water. The transfer of hydration water into bulk water increased the total compressibility of the solution, reducing the ultrasonic velocity. The aggregation of humic particles and the formation of rigid structures in systems with concentrations higher than 1 g·dm-3 was detected.

Characterization of pH-fractionated humic acids with respect to their dissociation behaviour.

Humic acids were divided into several fractions using buffer solutions as extraction agents with different pH values. Two methods of fractionation were used. The first one was subsequent dissolution of bulk humic acids in buffers adjusted to different pH. The second one was sequential dissolution in buffers with increasing pH values. Experimental data were compared with hypothesis of partial solubility of humic acids in aqueous solutions. Behaviour of humic fractions obtained by sequential dissolution, original bulk sample and residual fractions obtained by subsequent dissolution at pH 10 and 12 agrees with the hypothesis. Results demonstrated that regardless the common mechanism, solubility and dissociation degree of various humic fractions may be very different and can be estimated using parameters of the model based on the proposed mechanism. Presented results suggest that dissolving of solid humic acids in water environment is more complex than conventional solubility behaviour of sparingly soluble solids.

On the role of humic acids' carboxyl groups in the binding of charged organic compounds.

Interactions of humic acids (HAs) with two cationic dyes (methylene blue and rhodamine 6G) were studied using a unique combination of diffusion and partitioning studies in HAs, containing hydrogels and batch sorption experiments. In order to investigate the involvement of carboxyl groups of HAs in these interactions, all experiments were performed for both, the original lignite HAs and HAs with selectively methylated carboxyls. The results of the diffusion experiments confirm that the interactions between the solute and humic substances have a strong impact on the rate of diffusion process. Surprisingly, the effect is almost equally approved for original and methylated HAs. On the other hand, the results of batch sorption experiments show strong improvement of the sorption capacity (methylated HAs), which is explained by changed morphology of alkylated HAs. The comparison of the results of diffusion and adsorption experiments shows that the diffusion experiments simulate the transport of solutes in natural humics containing environment more reasonably.