Oxygen-flask combustion of accumulated organophosphorus pesticides for monitoring water pollution

A procedure is described for the determination of the total concentration of organophosphorus pesticides in aqueous solution based on conversion of the compounds to orthophosphoric acid by oxygen-flask combustion and spectrophotometric determination as phosphomolybdenum blue. The procedure is particularly sensitive when preceded by efficient and selective accumulation of pesticides. The adsorption of malathion, parathion and phosalone on Amberlite XAD-4 resin from 1 l of 7–36 μM water solutions, followed by combustion of 500 μl of eluate yields of orthophosphoric acid with 90–105% recoveries. The detection limit is ca. 150 ng ml^?1 pesticide in an aqueous sample. Inorganic phosphates and most of some commonly present non-pesticide phosphorus compounds are eliminated from the water sample during the adsorption step. In combination with a test for monitoring traces of cholinesterase inhibitors in surface waters, the determination of the total amount of organophosphorus pesticides as a cumulative parameter offers reliable information on the pollution level of the water environment. Application of such a combined procedure to a pond water from an apple orchard showed good correlation between phosphrus content and the cholinesterase inhibition.     

The surface chelate effect

The presence of a surface chelate effect is established in the model system of Cu2+ adsorption on a self-assembled monolayer of 16-mercaptohexadecanoic acid (MHA) on Au. The formation constant of Cu2+ with the MHA surface was found to be 119 +/- 3.2 times greater than that of Cu2+ with succinic acid (HOOC-(CH2)2-COOH), and 213 +/- 4.0 times greater than that of Cu2+ with glutaric acid (HOOC-(CH2)3-COOH) in aqueous solutions. Both of these molecules are known to chelate to metal ions forming seven- and eight-membered rings. The greater surface chelate effect is attributed to the presence of the two-dimensional array of ligands on the surface. We believe the surface chelate effect demonstrated here is of general significance to adsorption on molecular surfaces and should depend strongly on chemical functionality and monolayer structure.     

Impact of an error in the column hold-up time for correct adsorption isotherm determination in chromatography I. Even a small error can lead to a misunderstanding of the retention mechanism

The impact of a realistic error in the column hold-up time on the determination of the adsorption isotherm model was systematically investigated. Frontal analysis and the inverse method were used for the accurate determination of the adsorption isotherm. The true retention times of the breakthrough curves were used with a known hold-up time as reference. The adsorption isotherms were calculated using the same procedure that is used for real experimental adsorption isotherms, where the true hold-up time is unknown. The raw data were analyzed with calculations of adsorption energy distributions (AEDs), Scatchard plots, fitting to different rival adsorption models and finally their ability to predict true profiles. The results show that for a true Langmuir and bi-Langmuir model with an underestimated hold-up time the error may lead to a more heterogeneous model and for overestimated cases false adsorption processes like multi-layer adsorption or solute-solute interaction are assumed. The Scatchard plots for data obtained using a Langmuir adsorption isotherm are nonlinear and the AEDs show clear deviations from Langmuir behavior already at small deviations from the true hold-up time at a moderate surface coverage. The inverse method confirms the result that was obtained from the frontal analysis procedure.     

A Test Method for the Determination of Mercury(I, II) on a Polymer Surface

It was found that mercury(I, II) reacts with 5-chloro-2-hydroxy-3-[(tetrahydro-2,4-dithioxo-1,3-thiazin-5-yl)azo]benzenesulphonic acid (tyrodine) in weakly acid solutions in the presence of acetates, formates, and some organic solvents (ethanol and acetone) to give an intensely colored insoluble compound (_max = 600 nm, > 3 × 10⁴). The composition of the solution affected the sensitivity of the color reaction between mercury and tyrodine. A test procedure was developed for the determination of mercury(I, II) on the surface of a polycaproamide membrane with a detection limit of <50 ng in the adsorbent zone. The procedure involves the quantitative and selective adsorption of the mercury complex of tyrodine on the support surface from 0.5 M acetate solutions of pH 3–4 in the dynamic mode; the sample volume was 5–25 mL. Mercury was then determined by the change in the support color using a color scale or by the change in diffuse reflectance at 600 nm. The adsorption of the mercury complex was accompanied by an abrupt change in the color of the support surface from pale crimson (reagent) to stable blue-violet. The test procedure was used in the analysis of an industrial sample of complex composition with a mercury concentration of lower than 0.05%. The determination error (relative standard deviation) was 20%.     

Radiochemical purification of microgram and sub-microgram amounts of beryllium

A method is presented for the separation and radiochemical purification of microgram and tracer amounts of beryllium from solutions. It is a four-stage ion-exchange procedure consisting of (1) selective adsorption of the beryllium onto NaDAP resin and its elution with ammonium fluoride, (2) adsorption of the fluoroberyllate complex onto an anion-exchange column and elution of the beryllium with hydrochloric acid, (3) adsorption and selective elution of the beryllium on a cation-exchange column and (4) a pass through an anion-exchange column in concentrated hydrochloric acid. The method is quantitative and requires no carrier. Decontamination factors from most radionuclides tested were greater than 10,000. The method can be used to determine beryllium-10 in environmental materials.     

Investigation of adsorption of nanogram quantities of iron(II) tris-(1,10-phenanthrolinate) on glasses and silica by thermal lens spectrometry

Thermal lens spectrometry is used for studying adsorption equilibria in aqueous solutions at the level of nanogram quantities of iron(II) tris-(1,10-phenanthrolinate) as a model system. The kinetics of the sorption of the chelate on silica is studied and adsorption isotherms are built. Thermal lensing is used as a method for direct determination of the chelate concentration adsorbed on a quartz surface. The detected amount is 4.1×10⁻¹⁵ mol at the area irradiated by the excitation beam. The adsorption of iron(II) tris-(1,10-phenanthrolinate) on laboratory glassware at the nanogram level is characterised by measuring the residual concentration of the sorbate in solution. A procedure for handling and cleaning the laboratory glassware for determining nanogram amounts of iron in aqueous solutions is proposed. The sensitivity of thermal lensing both in measuring adsorption on silica and glass and quartz surfaces is 100-fold higher than diffuse-reflectance measurements under the same conditions.     

Measurement of ascorbic acid in single human neutrophils by capillary zone electrophoresis with electrochemical detection

A method has been developed for the determination of ascorbic acid (AA) in individual human neutrophils by capillary zone electrophoresis with electrochemical detection at a carbon fiber microdisk bundle electrode. The natively easily oxidized substances such as glutathione, dopa, dopamine, serotonin, epinephrine do not interfere with the determination of ascorbic acid. A procedure of treating capillaries, which can overcome the influence of the adsorption of the substances in cells on the inner surface wall of the capillary on the migration time and the number of theoretical plates of interests, has been described. The average amount of AA in an individual neutrophil is 0.557 fmol, which is consistent with the literature value.     

Adsorption–Photometric Determination of Cationic Surfactant Traces

A procedure has been developed for the adsorption–photometric determination of cationic surfactants in natural water. The procedure is based on the adsorption preconcentration of the cationic surfactants on silica gel, the reaction of the concentrate with the anionic reagent bromothymol blue to form ion pairs on a solid surface, and the photometric determination of excess bromothymol blue in solution. The analytical range is (0.5–5) × 10^–5 M for a 50-mL sample.     

Adsorption kinetics of surfactant mixtures from micellar solutions as studied by maximum bubble pressure technique

The adsorption kinetics of micellar solutions of anionic/cationic SDS/DATB mixtures with mixing ratios of 10/1 and 10/2, respectively, are studied experimentally by means of the maximum bubble pressure method. For long adsorption times the adsorption of the highly surface-active anionic/cationic complex leads to a decrease of dynamic surface tension in comparison to the single SDS system. However, the situation is the reverse for short adsorption times where the dynamic surface tension is increased by addition of the cationic surfactant, although the overall concentration is increased. This unexpected behavior is explained by partial solubilization of free SDS molecules into micelles formed by SDS/DTAB complexes. With increasing overall concentration, when eventually the CMC of SDS is reached, the anionic/cationic complex itself is solubilized by SDS micelles. Finally, no complex micelles, which for their part can solubilize an excess of SDS molecules, are present. Hence, the dynamic properties of the solution are no longer influenced by the depletion of SDS molecules and the mixture tends to behave like a pure SDS solution.     

Crystallization of organic crystals with "tailor-made" inhibitors. Determination of L-lysine using L-glutamic acid as substrate

A very simple turbidimetric procedure is used for determination of L-lysine, based on its inhibitory action on the crystallization of L-glutamic acid. The obtention of supersaturated solutions of L-glutamic acid was accomplished by means of the change in the solvent composition. Thus, the addition of ethanol to stable aqueous solutions of this amino acid allows the obtainment of unstable supersaturated solutions. The method suffers from very few interferences and permits the development of an analytical procedure to determine L-lysine in the presence of D-lysine. The method was also applied to the determination of L-lysine in pharmaceutical products.     

Oleic acid adsorption-desorption isotherms on the surface of high-dispersity ferrites from a solution in carbon tetrachloride

The equilibrium adsorption method was used to comparatively study the adsorption-desorption isotherms of oleic acid on the surfaces of manganese and copper ferrites from a solution in carbon tetrachloride. The adsorption isotherms of the fatty acid were described in terms of the theory of volume filling of micropores. The theory was used to calculate the limiting adsorption values, characteristic energy, and porous space volumes. The isotherm of oleic acid adsorption on the surface of manganese ferrite from a solution in carbon tetrachloride was similar to the isotherms of fatty acid adsorption from solutions in heptane, whereas the isotherm of adsorption on the surface of copper ferrite was similar to the isotherms of fatty acid adsorption from hexane. The limiting adsorption from carbon tetrachloride was higher on the surface of manganese ferrite than on the surface of copper ferrite. The adsorption-desorption isotherms contained hysteresis loops.     

Determination of uranium by fluorescence method

The paper describes a procedure for the determination of uranium in dilute solutions by fluorescence method. Factors influencing the determination in a phosphoric acid medium were studied. The detection limit of uranium determination is 0.04–0.05 ppm.     

Determination of the surface tension of surfactant solutions applying the method of Lecomte du Noüy (ring tensiometer)

Summary Starting from a comparative assessment of the outstanding works on the ring method (du Noüy) for the determination of the surface tension of liquids and its solutions it is shown that the application of this method to surfactant solutions can lead to substantial errors if one follows conventional conditions. These errors are mainly connected with so far unknown phenomena occurring during the raising of the ring and concerning the influence of the hydrophilic vessel wall above the solution level and the stretching of the solution surface. This is demonstrated quantitatively with surfactant solutions of different kind and concentration. These effects can be explained theoretically very simply by introducing certain assumptions on the behaviour of a surfactant adsorption layer on the inner vessel wall. Conditions leading to the elimination of these errors are given, thus enabling the application of the ring method to the determination of the surface tension of surfactant solutions.With 10 figures and 3 tables     

An adsorption method for semiquantitative determińation of coloured materials in very dilute solution

An adsorption method was developed for semiquantitative determination of very dilute, “colourless” solutions of coloured materials. Concentrating the coloured material by means of isothermal equilibrium, adsorption on an adsorbent of a limited surface area and thickness, visibly coloured surfaces are obtained which, by direct colorimetric measurements in diffusely reflected light, using the reference curve, can be employed for determination of unknown, concentrations.     

Estimation of Adsorption Layer Capacity by Sandwich Thin-Layer Chromatography

Abstract

The use of sandwich tanks with a capillary solvent delivery system permits the determination of the volume of the developing solvent in the adsorbent layer as well as the position of the solvent demixing front. Therefore, the adsorption isotherms of polar solvents from solutions in nonpolar diluents and the adsorption layer capacities can be determined in a simple manner, analogous to the column technique: Instead of determination of breakthrough volume, the solvent demixing front on the thin layer is localized by means of a series of test dyes whose spots flatten and merge on the steep solvent composition gradient. The method is illustrated for nine aliphatic ketones adsorbed from heptane and benzene solutions. The experimental results indicate different modes of adsorption from solutions in the two diluents; the surface areas corresponding to one solute molecule are also different for symmetrical dialkyl ketones and isomeric methyl-alkyl ketones.     

Fast prototyping of hydrophobic disposable polymer support arrays for matrix-assisted laser desorption/ionization-time of flight-mass spectrometry of proteins by atmospheric molding

A fast protocol for prototyping hydrophobic disposable poly(alkyl methacrylate-co-methyl methacrylate) copolymer sample support arrays for matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) of proteins by atmospheric molding is introduced. The sample support arrays were replicated by molding prepolymer alkyl methacrylate solutions into sandwich molds containing a micromachined silicon master, an aluminum spacer, and glass cover plates, followed by UV-initiated in situ polymerization under atmospheric pressure. The fabrication procedure enables a simultaneous fabrication/modification of single-use polymer arrays by a targeted selection of functional groups of the copolymerized monomers during molding. The one-step modification during the fabrication is demonstrated for enhanced protein adsorption to the modified materials by introduction of hydrophobic butyl-, dodecyl-, and octadecyl groups to the polymer backbone without a need for additional surface coating or derivatization. The MALDI-MS performance of the new polymer chips was tested for spectral measurements of bovine pancreas insulin, horse heart myoglobin, and bovine serum albumin. The protein adsorption to the new hydrophobic copolymer chips was studied for bovine pancreas trypsinogen; the sample desalting parameters, such as time and volume, were optimized for myoglobin as model proteins. A significant signal increase was achieved after efficient desalting of an insect Delta11-desaturase membrane protein fragment from a complex elution buffer (100 mM phosphate, 10 mM tris(hydroxyethyl)aminomethane, 0.5 M NaCl, and 10 mM ethylenediamine tetraacetic acid) on the poly(butyl methacrylate-co-methyl methacrylate) copolymer chip (monomer ratio 8:2 v/v) by simply washing the target zones. The new chips offer reduced sample manipulation and device fabrication times as well as simple operation.     

Electrocatalytic oxidation of ascorbic acid and voltammetric determination with a ferrocene-modified platinum electrode

Ferrocene attached to the surface of a platinum electrode catalyses the electrochemical oxidation of ascorbic acid in acidic buffer solutions. The overpotential for ascorbic acid oxidation is decreased by 150 mV at pH 2.2 compared with reaction at bare platinum; and an increase in anodic current and decrease in cathodic current for the redox reaction of ferrocene occurs on addition of ascorbic acid to the solution. The ferrocene-modified electrode is useful for the voltammetric determination of ascorbic acid in natural fruit juices. The advantages result from the electrocatalytic effect and from the prevention of adsorption of inhibitory substances from solution.     

Cathodic adsorptive stripping voltammetry of 6-thiopurine in absence and presence of some metal ions

Summary Cathodic stripping voltammetry of an adsorbed 6-thiopurine at HMDE was investigated in solutions of varying pH. A rapid and sensitive differential pulse voltammetric method was selected for its trace determination. A method has also been developed for the determination of 6-thiopurine in presence of Cu(II), due to the strong adsorption of the Cu-6-thiopurine complex at the surface of the HMDE and subsequent reduction of the surface-bound complex. A detection limit of 9.9×10^–9 mol/l was achieved in presence of Cu(II) and the slope of the straight line was seven times the slope in absence of Cu(II). Cathodic adsorptive stripping (CAS) voltammetry of 6-thiopurine in presence of Ni(II), Pb(II), Cd(II), and Fe(III) was also investigated. The influence of several operational parameters has been considered. Statistical analysis of the calibration curve data is included.     

Interaction between thallium(III) bromide and dicyclohexano-18-crown-6 immobilized on silica

The adsorption of cis-syn-cis-dicyclohexano-18-crown-6 on silica gel from organic solvents was studied. In the adsorption from chloroform solutions, the immobilization of the reagent molecules at the surface was coplanar. Hydrogen bonds between surface silanol groups and oxygen atoms of the polyether ring of the crown ether play an important role in the immobilization of the reagent. The reaction between thallium(III) bromide and the immobilized reagent was studied. The composition of complex compounds formed at the surface of the modified adsorbent was found. A procedure was proposed for the sorption-spectrophotometric determination of thallium(III) (≥0.05 mg/L) in the presence of heavy metal ions.     

Adsorption and rheological characteristics of humic acid salts at liquid-gas interfaces

Du Noöy ring and oscillating droplet methods are used to study the adsorption and dilatation rheological characteristics (viscoelastic modulus and phase angle) of aqueous solutions of humic acid salts at liquid-gas interfaces. It is established that the equilibrium surface tension and limiting surface elasticity of humic acid salt solutions are in good agreement with the model of a real two-dimensional solution that was previously proposed for biopolymers. Based on the results of analyzing dynamic surface tension and adsorption kinetics, it is shown that humic acid salts are characterized by a nondiffusion (barrier) adsorption mechanism.