Neutron Activation Analysis of Bottom and Fly Oil Ash Leachates

Seven samples of oil fly and bottom ashes were leached with water using a Canadian standard test method for shake extraction of solid waste. The concentrations of 20 elements in the leachates were determined by the computerized systematic instrumental absolute neutron activation analysis. The ranges of concentrations (in ppm) found for the elements in the leachates were: Al (3–526), Ba (0.5–6), Ca (100–695), Cl (13–59), Co (1–6.3), Cr (0.2–6.6), Cs (0.03–0.4), Eu (0.003–0.01), Fe (28–690), K (42–464), La (0.3–49), Mg (214–3150), Mn (1.2–20), Na (88–4050), Sb (0.04–0.4), Sc (0.003–0.07), Sr (1.2–23), U (0.07–1), V (1.2–4540) and Zn (2.3–200). These findings were compared with the maximum concentrations allowed for these elements by Canadian regulations. The concentrations of Cr and U were found to be higher than their permissible limits on 7 occasions. The purpose of this study was to determine the background levels of different elements in oil ash leachates, in order to evaluate their potential impact on underground water.     

Voltammetric Determination of Sulfide Ions

Procedures were proposed for the voltammetric determination of S^2– at a mercury-film electrode. They are based on the oxidation of S^2– at –0.79 to –0.80 V and on the reduction of HgS, the product of the oxidation of S^2–, at –0.76 to –0.96 V in a 1 M NaOH solution. The anodic and cathodic currents are linear functions of S^2– concentration in the ranges from 1 × 10^–5 to 1 × 10^–4 M and from 2 × 10^–6 to 1 × 10^–4 M, respectively.     

Redox chemistry of 1,2-dihydroxynaphthalene, 1,2-naphthosemiquinone and 1,2-naphthoquinone and their complexes with manganese(II) and manganese(III)

Cyclic voltammetry and controlled-potential electrolyses were carried out on solutions of 1,2-naphthoquinone (1,2-NQ), 1,2-dihydroxynaphthalene [1,2-Di(OH)-Cat] and their reduction and oxidation products in dimethyl sulfoxide. A study of the interaction of these species with MnII and MnIII has been undertaken. The complexes MnIII(Cat2–)33–, MnII(Cat2–)22– and MnII-(Cat2–), where Cat2– represents the dianion of 1,2-dihydroxynaphthalene, were obtained in solution and the species MnIISQ has been detected only on the surface of the electrode. An attempt to obtain the latter complex quantitatively caused intramolecular charge-transfer yielding the more stable MnIII-catechol complex. The MnIII–semiquinone complex is unstable and the ligand is easily oxidized. The charge-transfer reaction between MnIII(Cat2–)33– and MnII(Cat2–)22– is observed at –0.54/–0.52 V versus s.c.e. whereas the MnII complexes are reduced beyond the electrochemical window (at a potential more negative than –2.00 V versus s.c.e). On the other hand, all these species are destroyed when the coordinated ligand is oxidized. U.v.-vis. spectroscopy and magnetic susceptibility measurements were performed on the compounds in solution in order to characterize and to confirm the oxidation states of the metal ion in the species.     

Neutron activation analysis of asbestos from Canada

Concentrations of Al, Au, Br, Ce, Cl, Co, Cr, Fe, K, La, Mg, Mn, Na, Ni, Sb, Sc, Sm, Srm and V were determined in 6 samples of asbestos from Canada. They were equal to (in ppm): Al 1660–3430; Au 0.03–0.04; Br 3.1–11.7; Ce 1.7–4.8; Cl 116–331; Co 35–83; Cr 200–2060; Fe 29300–42200; K 125–867; La 0.28–1.03; Mg 24–25.9%; Mn 418–545; Na 364–1610; Sb 0.65–1.46; Sc 3.73–5.57; Sm 0.09–0.3; Sr 26.7–41.4; V 8.4–14.3. Five toxic elements were found in asbestos; Cr, Mn, Ni, Sb and V.     

Tungstate-Selective Electrode

A chemical sensor for tungstate ions has been developed and implemented in two versions on the basis of the poorly soluble nickel(II) hexatungstonickelate(II) heteropoly compound. The electrode function is linear within the range 10^–5–10^–1 M tungsten for the film electrode and within the range 10^–4–10^–1 M tungsten for the coated wire electrode at pH 6–9. The slope of the electrode function is 28–29 mV. The time it takes to attain an equilibrium electrode potential is 1–5 min, depending on the ion concentration to be determined. The selectivity coefficients are found for the tungstate-selective electrode in the presence of chloride, sulfate, nitrate, and perchlorate.     

Voltammetric Determination of Rubeanic Acid

Procedures for the voltammetric determination of rubeanic acid (RA) at a mercury-film electrode were proposed. They are based on the oxidation of RA at –0.70 to –0.80 V or on the reduction of mercury sulfide, the product of RA oxidation, at –0.82 to –0.85 V (versus a saturated silver–silver chloride electrode) in a 1 M NaOH solution. The oxidation and reduction currents are linear functions of RA concentration in the ranges from 9 × 10^–6 to 3 × 10^–4 M and from 5 × 10^–6 to 3 × 10^–4 M, respectively.     

Development of an amperometric biosensor based on covalent immobilization of tyrosinase on a boron-doped diamond electrode

An amperometric enzyme electrode based on direct covalent immobilization of tyrosinase on a boron-doped diamond (BDD) electrode has been developed for the detection of phenolic compounds. Combined chemical and electrochemical modifications of the BDD film with 4-nitrobenzenediazonium tetrafluoroborate, an aminophenyl-modified BDD (AP–BDD) surface was produced, and then the tyrosinase was covalently immobilized on the BDD surface via carbodiimide coupling. The response dependences of the enzyme electrode (Tyr–AP–BDD electrode) on pH of solution, applied potential, oxygen level and phenolic compounds diffusion were studied. The Tyr–AP–BDD electrode shows a linear response range of 1–200, 1–200 and 1–250 μM and sensitivity of 232.5, 636.7 and 385.8 mA M⁻¹ cm⁻² for phenol, p-cresol and 4-chlorophenol, respectively. 90 percent of the enzyme activity of the Tyr–AP–BDD electrode is retained for 5 weeks storing in 0.1 M PBS (pH 6.5) at 4 °C.     

Effect of using mixed ion-pairs on PVC-membrane electrodes for ephedrine

Mixed ion-pairs based on the use of ephedrinium (EPH)-TPB plus EPH-reineckate (II) and phenylephrine-TPB plus EPH-reineckate (III) were tried for use in plastic membranes. The results were compared to those of an EPH-reineckate (I) single ion-pair electrode. The Nernstian slopes were 50, 49 and 55 mV decade^–1 for membranes I, II and III, respectively. The linear concentration ranges were 10^–5–10^–1, 4.0 × 10^–5–10^–1 and 6.3 ×^–5–10^–1 M ephedrine. The detection limits were 4 ×^–6,10^–5 and 1.2 × 10^–5 M ephedrine for membranes I, II and III, respectively. The pH ranges were 4–9, 3–9 and 2–8 for I, II and III-membranes, respectively. Selectivity coefficient values for membrane II were better than those for membranes I and III. The effects of increasing KC1 concentration and temperature changes were explained for the three electrodes. The isothermal temperature coefficients were 0.00145, 0.0007 and 0.00055 V/ °C for electrodes I, II and III. Electrode III was applied for the determination of ephedrine in its pharmeaceutical preparations with an overall relative standard deviation range of 1.3–2.4% and an overall mean recovery value of 98.1%.     

ZnO nanorods decorated calcined Mg–Al layered double hydroxides as photocatalysts with a high adsorptive capacity

The nanocomposites of magnesium–aluminium–carbonate–layered double hydroxides (Mg–Al–CO₃–LDHs) and ZnO nanorods were prepared via a homogeneous precipitation process. The presence of ZnO nanorods made the calcined Mg–Al–CO₃–LDHs, the strong adsorptive adsorbents for anions, have a photocatalytic activity. Both Mg–Al–CO₃–LDHs and the nanocomposites with various ZnO/Mg–Al–CO₃–LDHs mass ratios from 0.5:1 to 3:1 were characterized by X-ray diffraction, transmission electron microscope and UV–vis diffuse reflectance spectra. The nanocomposites quickly adsorbed the anionic dyes such as acid red G (ARG) without the light illumination, and the adsorbed dyes on the recovered nanocomposites were then degraded in a separated photocatalytic reactor. The adsorption ability of the nanocomposites and their photocatalytic activities for the removal of ARG were evaluated by the Fourier transform infrared spectra and UV–vis extinction spectra. The sample at 3:1 ZnO/Mg–Al–CO₃–LDHs mass ratio was shown to have higher photocatalytic efficiencies.     

Towards the understanding of the spectroscopic behaviour of the C–H oscillator in C–HO hydrogen bonds: the effect of solvent polarity

The effect of solvent polarity versus specific C–HO contacts on the vibrational νC–H mode is studied using CHCl₃ as a model system. Ab initio SCI–PCM calculations show that the overall shift of the νC–H band, sometimes ascribed to the C–HO hydrogen bonding, can in fact be explained by the electrostatic interaction with a dielectric environment. The presence of a new νC–H band – assigned to the C–HO bonded forms – remains as the most reliable evidence of C–HO hydrogen bonding.     

Redox-iodometry: a new potentiometric method

A new iodometric method for quantifying aqueous solutions of iodide-oxidizing and iodine-reducing substances, as well as plain iodine/iodide solutions, is presented. It is based on the redox potential of said solutions after reaction with iodide (or iodine) of known initial concentration. Calibration of the system and calculations of unknown concentrations was performed on the basis of developed algorithms and simple GWBASIC-programs. The method is distinguished by a short analysis time (2–3 min) and a simple instrumentation consisting of pH/mV meter, platinum and reference electrodes. In general the feasible concentration range encompasses 0.1 to 10^–6 mol/L, although it goes down to 10^–8 mol/L (0.001 mg Cl₂/L) for oxidants like active chlorine compounds. The calculated imprecision and inaccuracy of the method were found to be 0.4–0.9% and 0.3–0.8%, respectively, resulting in a total error of 0.5–1.2%. Based on the experiments, average imprecisions of 1.0–1.5% at c(Ox)>10^–5 M, 1.5–3% at 10^–5 to 10^–7 M, and 4–7% at <10^–7 M were found. Redox-iodometry is a simple, precise, and time-saving substitute for the more laborious and expensive iodometric titration method, which, like other well-established colorimetric procedures, is clearly outbalanced at low concentrations; this underlines the practical importance of redox-iodometry.

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An erratum to this article is available at .     

Potential-Dependent Adsorption of Transferring Ions Having Asymmetric Charge Distribution at the 1,2-Dichloroethane|Water Interface and Its Ion-Transfer Kinetics Studied by AC-modulated Voltfluorometry

The kinetics of the transfer of Erythrosine B dianions (EB^2–) and Eosin Y dianions (EY^2–) across the 1,2-dichloroethane|water interface, studied using ac-modulated voltfluorometry, is compared with that of Rose Bengal dianions (RB^2–). All three exhibit anomalous phase angles, showing the transient adsorption of these ions at the interface. The apparent standard rate constants are 9.0 × 10^–3 and 1.3 × 10^–2 cm s^–1 for EY^2– and EB^2– at 25° (cp. 1.4 × 10^–2 cm s^–1 for RB^2–). The slight decrease in the rate in the order RB^2–, EB^2–, and EY^2– may be associated with the increasing polarity of the ions, which endows the ions with a stronger interaction with water, resulting in the slower rotational dynamics of the ions on crossing the interface.     

Trace element determination in seawater by ICP-SFMS coupled with a microflow nebulization/desolvation system

Direct and simultaneous determination of Al, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, U, V and Zn in diluted (1:10 v:v) seawater from the Antarctic Ocean and the Venice Lagoon at the ng mL^–1 and pg mL^–1 level has been performed by using an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Samples were analysed by using a PFA microflow nebulizer coupled with a desolvation system or a PFA microflow nebulizer coupled with a Teflon spray chamber, respectively. Measurements were carried out at low (LR, m/m=300), medium (MR, m/m=3,000) and high (HR, m/m=7,500) resolutions depending on the studied isotope. To avoid contamination, sample pre-treatment was carried out in a clean laboratory equipped with a Class 100 vertical laminar flow hood. Concentration ranges (minimum–maximum in ng mL^–1) found in the Antarctic seawater samples (in depth profiles) were: Ag 0.0004–0.0018, As 0.69–1.32, Cd 0.031–0.096, Co 0.018–0.065, Cr 0.18–0.46, Cu 0.04–1.58, Fe 0.13–1.63, Mn 0.02–0.12, Mo 5.97–12.46, Pb 0.007–0.074, Sb 0.033–0.088, U 0.5–1.9, V 0.6–2.5 and Zn 0.16–0.80. Concentration ranges (min–max in ng mL^–1) found in the Venice Lagoon water samples (temporal profile from a benthic chamber experiment) were: Al 0.24–0.61, Ag 0.007–0.031, As 1.42–2.27, Cd 0.050–0.182, Co 0.440–1.461, Cr 0.15–0.34, Cu 0.81–2.46, Fe 0.25–1.66, Mn 11.6–31.7, Mo 6.50–10.6, Pb 0.047–0.225, Sb 0.240–0.492, U 1.7–3.3, V 1.3–2.8 and Zn 5.20–21.5. The detection limits range between 0.06 pg mL^–1 for Ag and U to 15 pg mL^–1 for Fe. In order to check the accuracy of the analytical procedure, measurements of the trace elements in a certified reference material (coastal Atlantic seawater, CASS-4-NRCC) were compared with the certified values. In addition, the results from the Antarctic and Venice Lagoon samples were compared with those obtained by using different analytical techniques.     

In situ study on the effects of Ni and Mo on the passive film formed on Fe–20Cr alloys by photoelectrochemical and Mott–Schottky techniques

Effects of alloying elements (Ni and Mo) on the structure of passive film formed on Fe–20Cr alloys in pH 8.5 buffer solution were explored by analyzing the in situ electronic properties measured using the photoelectrochemical technique and Mott–Schottky analysis. The passive film formed on Fe–20Cr–10Ni was found to be mainly composed of Cr-substituted γ-Fe₂O₃ from similarities in photocurrent response for the passive films formed on the alloy and Fe–20Cr. On the other hand, the photocurrent spectra for the passive films of Fe–20Cr–15Ni–(0, 4)Mo alloys exhibited the spectral components associated with NiO and Mo oxide (MoO₂ and/or MoO₃) in addition to that induced by Cr-substituted γ-Fe₂O₃. Mott–Schottky plots for the passive films formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo confirmed that the passive films on Fe–20Cr–(10, 15)Ni–(0, 4)Mo alloys have a base structure of Cr-substituted γ-Fe₂O₃ with variation of densities of shallow and deep donors depending on the Ni and Mo contents in the alloys. We suggest that the passive film formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo alloys are composed of (Cr, Ni, Mo)-substituted γ-Fe₂O₃ when the concentrations of Ni and Mo are below critical values. However, NiO and Mo oxide (MoO₂ and/or MoO₃) would be precipitated in the passive films when the concentrations of Ni and Mo exceed critical values.     

Deposition behaviors and patterning of TiO2 thin films on different SAMs surfaces from titanium sulfate aqueous solution

Patterning of TiO₂ thin films was successfully obtained on different self-assembled monolayers (SAMs) in aqueous solution by micro-contact printing (μCP) method. The substrates were immersed in an aqueous solution containing titanium sulfate (Ti(SO₄)₂) and hydrogen peroxide for deposition at 80 °C. The growth rates on various surfaces were as follows: sulfonic (–SO₃H) > amino (–NH₂) > methyl (–CH₃) > hydroxyl (–OH). According to the XPS results, SAMs with the terminal groups of –SO₃H and –NH₂ were favorable for the deposition. The TiO₂ film deposited on the SAM with the terminal group of –CH₃ could be easily peeled off. Clearly, TiO₂ patterns were obtained on the prepatterned surfaces of –SO₃H/–CH₃ and –NH₂/–CH₃ SAMs. The deposition mechanism might be relevant to electrostatic interaction, Stern layer, lone pair electrons and Van der Vaals forces. The TiO₂ film was anatase after annealing at 500 °C and comprised particles with an average diameter of ca. 10 nm.     

Determination of trace europium by use of the new fluorescence system europium–sparfloxacin–1,10-phenanthroline–sodium dodecyl sulfate

A new lanthanide-sensitized luminescence system: europium–sparfloxacin–1,10-phenanthroline–sodium dodecyl sulfate has been discovered. The spectrofluorimetric properties of the system were studied. The effect of experimental conditions on the fluorescence intensity was defined. Under the optimum conditions, the fluorescence intensity of the system is a linear function of the concentration of europium in the range 5.0×10^–9–1.0×10^–6 mol L^–1 and the detection limit is 1.0×10^–10 mol L^–1. The system was used for the determination of trace amounts of europium in rare earth samples with satisfactory results.     

Synthesis,electrochemical and magnetic properties of new macrocyclic copper(II) complexes derived from 2,6-diacetyl-4-4-methylphenol

A series of binuclear macrocyclic copper(II) complexes [Cu2Lm,n](ClO4)2·xH2O have been prepared in which the two copper(II) ions are placed in two geometrically distinct co-ordination environments. The macrocycles with two 2,6-bis(iminomethyl)-4-methylphenol entities combined through two different lateral chains, –(–CH2–)–m and –(–CH2–)–n (m = 2 or 3, n = 2 to 5) were synthesized by stepwise cyclization. Cyclic voltammetry shows the presence of two reduction couples: CuIICuII CuICuII and CuIICuI CuICuI. The comproportionation constants, Kcom, for the mixed valence CuICuII complexes have been determined electrochemically. The Kcom value increases in the order of the macrocycles: (L2,2)^2–<(L2,3)^2–<(L2,4)^2–<(L2,5)^2– and (L3,3)^2–<(L3,4)^2–<(L3,5)^2–. Cryomagnetic investigations (80–300K) reveal a moderately strong antiferromagnetic spin exchange between the copper(II) ions within each complex (J = –210 to –390 cm–1).     

Multielement measurements in Mexican cigarette tobacco

The concentration of 21 elements in cigarette tobacco in nine different brands manufactured and commercially available in Mexico has been determined using neutron activation analysis. The concentration range of the measured elements (in g g^–1) were: As, (four brands) <0.55–3.24; Ba, 64–251; Br, (four brands) 49–136; Ce, <0.3–1.7; Co, 0.29–0.55; Cr, <0.8–2.4; Cs, 0.091–0.40; Eu, <0.03; Fe, 420–680; Hf, <0.03–0.13; K, (four brands) 18300–40300; La, (four brands) <0.2–0.66; Na, (four brands) 309–566; Rb, 19–50; Sb, <0.7; Sc, 0.13–0.22; Se, <0.7; Sm, (four brands) 0.07–0.14; Sr, 227–472; Th, <0.1–0.17 and Zn, 14–56. The results are compared with the literature values for the concentration of the above elements in cigarette tobacco from other countries.     

A study of the chemiluminescence behavior of myoglobin with luminol and its analytical applications

A chemiluminescence signal at 425 nm was observed when ferric state myoglobin was mixed with luminol in alkaline medium. Because the signal was remarkably enhanced in the presence of Fe(CN)₆ ^4–, analytical applications were investigated in a flow-injection system. The increase in chemiluminescence was linearly dependent on myoglobin concentration in the range 0.1 to 100 nmol L^–1, and the limit of detection was 0.04 nmol L^–1 with relative standard deviation 3.2% (3). It was also found that binding of Mb with the ligands CN^–, SCN^–, and F^– significantly inhibited the chemiluminescence reaction. The linear dynamic ranges for the ligands were 1.0–300.0, 0.1–3.0, and 0.5–100.0 nmol L^–1, and the limits of detection (S/N=3) 0.4, 0.04, and 0.2 nmol L^–1, for F^–, CN^–, and SCN^–, respectively. The relative standard deviations were 5.32%, 6.13%, and 3.38% for 0.1 nmol L^–1 CN^–, 0.5 nmol L^–1 SCN^–, and 1.0 nmol L^–1 F^–, respectively. At a flow rate of 2.0 mL min^–1 the assay could be accomplished in 1 min, including sampling and washing. The method has been successfully applied to the determination of myoglobin in human urine and F^– in water samples. A possible mechanism of chemiluminescence production by myoglobin and luminol is presented.     

Polarographic and voltammetric determination of trace amounts of 2-nitronaphthalene

The polarographic behaviour of 2-nitronaphthalene was investigated by DC tast polarography (DCTP) and differential pulse polarography (DPP), both at a dropping mercury electrode, and differential pulse voltammetry and adsorptive stripping voltammetry, both at a hanging mercury drop electrode. Optimum conditions have been found for the determination of 2-nitronaphthalene by the given methods in the concentration ranges of 2×10^–6–1×10^–4, 2×10^–7–1×10^–4, 1×10^–8–1×10^–4 and 2×10^–9–1×10^–8 M, respectively. Practical applicability of these techniques was demonstrated by the determination of 2-nitronaphthalene in drinking and river water after its preliminary separation and preconcentration using liquid–liquid and solid-phase extraction with limits of determination of 3×10^–10 M (drinking water) and 3×10^–9 M (river water).