Electromigration of chitosan D-glucosamine and oligomers in dilute aqueous solutions

The electromigration behavior of chitosan D-glucosamine and oligomers with a degree of polymerization from 1 to 6 in dilute aqueous systems containing either NaCl or KCl salt at 0.01, 0.05, and 0.1 M at pH values from 2 to 9 was evaluated. The results showed that the electromigration of the chitosan D-glucosamine and oligomers did not change by changing the type of salt in the running medium and that the pH had a significant effect on the direction of migration under an external electric field. In addition, the increase in the ionic strength of the medium caused a significant decrease on the absolute value of the electrophoretic mobility, and the highest values of the electromobility were observed in water. However, the ionic strength had no significant effect on the electrophoretic mobilities at pH 2 in comparison with the other pH values. The dimer showed the highest electrophoretic mobility in the alkaline zone of the pH. At pH values lower than the pKa of the D-glucosamine, the chitosan D-glucosamine, and oligomers migrated toward the anode, where the amine groups are protonated and carry positive charge. At higher pH values, chitosan D-glucosamine and oligomers migrated toward the anode, even though they did not carry any electric charge. The contribution of the difference in the dielectric constants between the solvent and the solute to this phenomenon was highlighted. It was shown that the glucose moiety contributes to the direction of migration of the chitosan D-glucosamine and oligomers under alkaline conditions and that the difference in the dielectric constant of glucose and the solvent accounts for the direction and the extent of electromobility.     

Determination of fluoride in fluoride tablets and solutions by ion-selective electrode: collaborative study

A proposed method using the fluoride (F) ion-selective electrode has been developed for determining the fluoride ion concentration in tablets and solutions containing sodium fluoride. The method has been subjected to collaborative study. Eight samples consisting of 2 authentic fluoride solutions, 2 commercial fluoride solutions, and 4 commercial fluoride tablets were sent to each of 11 collaborators together with a copy of the method. Single assays on the authentic fluoride solutions known to contain 1 mg F/5 mL were performed with average recoveries of 99.5 and 99.6% and relative coefficients of variation (CV) of 2.11 and 1.91%, respectively. Single assays of 2 commercial fluoride solutions declared at 1 mg F/5 mL gave mean values of 0.994 and 0.990 mg and relative CV values of 1.88 and 2.36%, respectively. Single assays of 2 commercial fluoride tablet preparations declared at 0.5 mg F gave mean values of 0.485 and 0.478 mg and relative CV values of 3.12 and 3.71%, respectively. Single assays of 2 commercial fluoride tablet preparations declared at 1 mg F gave mean values of 0.991 and 0.981 mg and relative CV values of 2.99 and 2.85%, respectively. The method has been adopted official first action.     

Stimulation of growth in papaya and other plants by dilute salt solutions

The growth of Solo papaya, Winter rye and Chinese cabbage is enhanced when they are cultivated in saline waters at 2500 to 3200 ppm total dissolved solids. Stimulation began at the germinating stage with rye and cabbage, but in the case of papaya only with 6 to 8 week old plants. The stimulation noted was not nutritionally based, as a complete nutrient was included.     

Determination of aluminium activity from measurements of fluoride in acid soil solutions

Trivalent aluminium (Al) in solutions extracted Centrifugally from soils with pH ranging from 3.3 to 5.8 in 0.01 M CaCl₂ was estimated from: (i) iterative computation using total Al (pyrocatechol violet), pH, major ions and Al ligands (PCV + GEOCHEM); (ii) 15-s reaction with 8-quinolinol (8Q); and (iii) electrode measurements of free and Al-complexed fluoride. Fluoride and hydroxyl complexes were major Al-components. With decreasing pH, complexed and total F increased along with Al, but free F decreased. Results from PCV + GEOCHEM and 8Q were consistent with each other and with solubilities of the clay minerals in the soils. Relative to these, the F-electrode method increasingly overestimated Al as pH increased and Al decreased; its evident failure was not attributable to La interference, OH interference, or the uncertainty of electrode calibration at F activities below 10^?6 M.     

Prolonged leaching of mineral forest soils with dilute HCl solutions: the solubility of Al and soil organic matter

Long-term acidification has been shown to result in a considerable decrease in the amount of organically bound soil Al and in a gradual decrease in the solubility of Al. We examined the solubility of soil organic matter (SOM) and Al in four acid mineral soils (one Arenosol Ah, two Podzol Bh, and one Podzol Bs) as they were leached sequentially using a solution containing 0.001 m HCl and 0.01 m KCl. The acid leaching resulted in relative decreases in Al that were 2–6 times greater than for organic C. The organic C and Al dissolved by the acid leaching originated mainly in the pyrophosphate-extractable fraction of the elements. Protonation seems to be a major mechanism in stabilizing the residual SOM, as indicated by small changes in effective cation exchange capacity with the degree of acid leaching. In the samples of Podzol Bh and Arenosol Ah soils the solubility of Al (defined as log₁₀{Al³⁺} + 1.5pH) in equilibrium suspensions (0.01 m KCl) was closely related to the ratio of pyrophosphate-extractable Al to pyrophosphate-extractable organic C. The Podzol Bs sample probably contained a small amount of a surface-reactive Al(OH)₃ phase, which rapidly became depleted by the acid leaching.     

Freeze-drying of soil clays

The crystallization of ice during preparation of soil clays for freeze-drying can cause aggregation of clay particles. This often results in sample loss by the ejection of material in the water vapour stream during sublimation. These undesirable effects are overcome with many soil clays by the addition of ethanol to a concentration of approximately 4% in the suspension before freezing. The structure of the clay body obtained by freeze-drying appears to depend mainly on the particle-size distribution of the clay; a more coherent structure being obtained from finer clays.     

Heat of immersion of soil allophanic clays

Amorphous soil inorganic materials, specifically allophane. are believed to have a marked effect on soil properties and soil productivity, even in a relatively small amount, due to their large specific surface area, peculiar nature of surface and high chemical reactivity. They seem be present in soils, more or less, but determination of their content is generally semiquantitative or not fully reliable, because allophane includes aluminosilicates in a wide range of chemical composition and of properties, and any satisfactory, quantitative analytical method has not been established.     

Interaction dynamics between a contaminated dredged sediment and extracting solutions of different nature

Purpose

The purpose of this work is to study the dynamics between the matrix of a contaminated marine sediment, its contaminants and various desorbing solutions by means of equilibrium tests, sedimentation trials and zeta potential, with the focus on assessing optimum enhancing solutions for decontamination purposes.

Materials and methods

The sediment samples were analysed to determine their physico-chemical characteristics: particle size distribution, solids concentration, total organic carbon (TOC), content of heavy metals, organic contaminants, mineralogical phases, zeta potential and buffer capacity. Twelve extracting solutions of different nature were used for equilibrium tests, in which the dynamic behaviour of the sediment was evaluated. Elemental analysis was carried out for the sediment samples and the solutions before and after the tests.

Results and discussion

The sediment was mainly composed of clay and lime, with a high content of iron, which has a strong influence on sorption-desorption processes. The sediment had a considerable buffer capacity at low and high pH values. The desorption of the metals was not proportional to pH. The highest decrease in the concentration of metals from the sediment was obtained with 0.2 M ethylenediaminetetra-acetic acid (EDTA) and 1 M nitric acid, while the lowest degree of metal extraction occurred in pure water and potassium iodide (KI).

Conclusions

The most important parameters for contaminant release were complexation ability of the solution for the sediment components and pH of the solution. A promising design for the remediation treatment for the investigated sediment includes complexation and strong acid agents.

     

Extraction of heavy metal ions sorbed on clays

The ability of seventeen different chemical solutions to displace heavy metal ions (Pb, Zn, Cu, Cd), pre-adsorbed on clay (kaolinite, illite and montmorillonite) at either pH 5 or 7, has been examined and the relative efficiency of each extractant ascertained. Of the reagents used, only EDTA (0.001 M, pH 7) quantitatively released all four ions from the three clays; oxalic acid (0.1 M, pH 3.3), totally displaced at least three ions from each clay. Other reagents, for example ammonium oxalate (0.1 M), ammonium nitrate (0.01 M), nitric acid (0.1 M) and sodium citrate (0.01 M) effectively displaced one or more heavy metal ions from individual clays. Near quantitative displacement by an excess of Na (0.1 M) or Ca (0.05 M) ions was observed only on montmorillonite. Pre-adsorption at pH 7 was accompanied by precipitation of excess metal ion, and the extraction efficiency in these systems was determined by the ability of the reagent to both dissolve hydrous oxide species and displace sorbed metal ions. The implications of the results with respect to the nature of the adsorption process and relevance to environmental systems have been considered.     

Aggregation in soils with small amounts of swelling clays. I. Aggregate stability

The respective role of organic materials and poorly-ordered Al and Fe hydrous oxides on soil aggregate stability was studied in silty soils with little swelling clay, using both multivariate analysis and physico-chemical approaches. Soil disaggregation is a function of the hydrophobic character of organic matter (OM), which depends on the nature of the organic materials, cationic environment and the aggregating effect of Al and Fe hydrous oxides.
Two kinds of aggregates >50 μm can be distinguished in organic soils, one being about six times more stable than the other. In soils poor in organic matter, weak aggregates dominate; the binding agents are Ca or Al OM rich in polysaccharides and peptides.     

The use of total ionic strength adjusting buffers in determining fluoride concentration in soil solutions by ion selective electrometry

Abstract

Total ionic strength buffers based on citrate at pH 7.5 and cyclohexylenediaminetetra‐acetic acid (CDTA) at pH 5.2 were evaluated for use when determining fluoride (F) concentration in soil solutions. Both buffers achieved acceptable recoveries of F added to ultra‐filtered (0.025 μm) solutions. Recovery of F added to unflltered and 0.22 μm filtered solution was low when the CDTA buffer was used. This effect was attributed to the adsorption of F by micro‐particulate materials present in these samples. The use of this buffer would need to be restricted to samples in which micro‐particulates were not present. The performance of the citrate buffer was not affected by the presence of microparticulates; however, electrode response times, and departure from Nernstian response at low F concentrations, were greater when this buffer was employed. Fluoride was found to be present at low concentrations in the soil solution of the 60 virgin highly weathered soils tested. The F concentration in 75% of the surface samples was <3 μM, while all subsoil samples had soil solution F concentrations <1 μM.     

Estimation of imogolite in soils and clays by DTA

Abstract

DTA (differential thermal analysis) was used on mixtures of allophane and imogolite, and a calibration curve for estimating imogolite was obtained using the height of the endothermic peak near 400°C. This peak occurs between 390°C to 430°C, is distinctive and can be used to estimate imogolite in clay fractions and soils. An endothermic peak near 470°C observed in some Andisols probably arises from dehydroxylation of hydrated glass.     

Effect of particle size of halloysite on the deflocculation of mutual flocs of allophane and halloysite at pH 6.5 in dilute xanthan polysaccharide solutions

The effect of the particle size of halloysite on the deflocculation of mutual floes of allophane and halloysite in the presence of anionic xanthan polysaccharide was investigated spectrophotometrically. Although allophane which flocculated at the i.e.p. (pH 6.5) exhibited polymeric (i) weak-stabilization (PWST), (li) flocculation (PFL), and (iii) stabilization (PST) with increasing addition of xanthan, allophane and halloysite which flocculated mutually at pH 6.5 inhibited the deflocculation, viz., PWST and PST. Halloysite with a smaller average particle size (i.e., 0.08,um in average diameter) than the suspended microaggregates (SMAs) of allophane inhibited significantly the deflocculation, suggesting that the halloysite particles flocculated around the allophane particles. Halloysite with a larger average particle size (i.e., 0.2 μn in average diameter) than the SMAs of allophane slightly inhibited the deflocculation, suggesting that the halloysite particles were attached to the center of the flocculated SMAs of allophane. The inhibitory effects of particle arrangements on the deflocculation of the mutual floes of allophane-montmorillonite and allophanekaolinite were also investigated comparatively.     

Equilibrium adsorption of isoproturon on soil and pure clays

The adsorption of isoproturon on soil and pure clay minerals has been investigated as a means of understanding its mobility in soils. Measured adsorption coefficients are correlated with soil and clay mineral properties. Soil organic matter controlled the adsorption of isoproturon at organic carbon contents exceeding 27 g kg^?1, whereas at less than this threshold, clay mineral surfaces appeared to control adsorption. The effect of varying temperature suggests that adsorption of isoproturon is a physical process. From the comparison of the fits of linear, Freundlich, and Langmuir adsorption isotherms to the data, the adsorption is best described as a partition process.     

Sorption and catalytic hydrolysis of diethatyl-ethyl on homoionic clays

Sorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were studied in aqueous media. The Freundlich sorption coefficient, K(f), measured from isotherms on clay followed the order of Na(+) approximately K(+) > Mg(2+) approximately Ca (2+). Analysis of FT-IR spectra of diethatyl-ethyl sorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for sorption, indicating that sorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by sorption on the clay surface.     

Correction to: Interaction dynamics between a contaminated dredged sediment and extracting solutions of different nature

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