Evaluation of focused ultrasound and ozonolysis as sample treatment for direct determination of mercury by FI-CV-AAS. Optimization of parameters by full factorial design

Different oxidation methodologies based on ozone and focused ultrasound for the degradation of organic matter and organic-mercury compounds (spiked) present in human urine are discussed. Inorganic and total mercury can be determined in human urine. A flow-injection cold-vapour atomic absorption spectrometer system was used for mercury measurements. Optimization of cold vapour generation was performed with NaBH4 and SnCl2. A two-level full factorial design (2(4)) was applied to understand the cross-effects among the variables influencing the degradation of organic-mercurials and organic matter in urine by KMnO4/HCl/focused ultrasound, namely, KMnO4 and HCl concentration, ultrasonication time and ultrasonication amplitude. Optimization results showed that all variables were significant. New trends in the application of focused ultrasound and ozone are highlighted. As a result of the optimization procedure, one simple, rapid and accurate method was developed for the determination of total mercury in urine samples The method is based on the ultrasound assisted degradation of organo-mercurials and organic matter in urine in the presence of KMnO4/HCl/Focused Ultrasound. The procedure can be accomplished within 3 min, using 50% sonication amplitude provided by a probe ultrasonic device (63 W maximum output power, 22.5 kHz frequency). The method was applied to measure the mercury content in spiked urine from different non-exposed volunteers.     

Definition and measurement of the normalized electrical impedance of lossy piezoelectric resonators for ultrasonic transducers

Relevant equivalent circuit parameters and values of material constants of a piezoelectric resonator can be determined from measurements of its electrical input impedance as a function of frequency. The complex electrical impedance curves and the associated critical frequencies are the basis of this characterization by the piezoelectric resonance method. In this paper, the previously introduced concept of normalized electrical impedance of the lossy resonator, extended to include piezoelectric losses, is applied to the analysis of the effects of different types of intrinsic losses on peak values, bandwidths and characteristic frequencies. The resulting impedance patterns depend solely on the electromechanical coupling coefficient and the loss tangents, providing a useful tool for the analysis of low-Q resonators. The normalized impedance is experimentally evaluated from the basic data provided by an HP 4194A impedance analyser by means of specifically developed ASP programs.     

Mercury determination by FI-CV-AAS after the degradation of organomercurials with the aid of an ultrasonic field: the important role of the hypochlorite ion

Due to new findings, the methodology based on room-temperature ultrasonic irradiation (sonolysis) for conversion of organomercurials into inorganic mercury [J.L. Capelo, I. Lavilla, C. Bendicho, Anal. Chem. 72 (2000) 4979-4984.] is further investigated. Inorganic mercury is selectively determined by Flow Injection-Cold Vapour Atomic Absorption Spectrometry (FI-CV-AAS) using SnCl₂/HCl. Complete oxidation of methyl-mercury can be accomplished within 90 s whilst phenyl and diphenyl-mercury can be degraded within 10 s using a 50% sonication amplitude (100 W nominal power) provided by a probe ultrasonic device (20.5 kHz frequency) and a 1 mol L⁻¹ HCl liquid medium with the presence of hypoclorite ion. The importance of hypochlorite in reduction of organomercurials by stannous chloride is highlighted. Oxidation kinetics indicated a pseudo first-order reaction for methyl-mercury, phenyl-mercury, and dipheny-mercury.     

Tandem focused ultrasound (TFU) combined with fast furnace analysis as an improved methodology for total mercury determination in human urine by electrothermal-atomic absorption spectrometry

A new sample preparation procedure based on tandem (that is, different diameter probe sonicators used in the same sample treatment) focused ultrasound (TFU) for mercury separation, preconcentration and back-extraction in aqueous solution from human urine has been developed. The urine is first oxidized with KMnO₄/HCl/focused ultrasound (6 mm probe). Secondly, the mercury is extracted and preconcentrated with dithizone and cyclohexane. Finally, the mercury is back-extracted and preconcentrated again with the aid of focused ultrasound (3 mm probe). The procedure allows determining mercury by electrothermal atomic absorption spectrometry with fast furnace analysis and calibration against aqueous standards. Matrix modification is provided by the chemicals used in the sample treatment. The procedure is accomplished with low sample volume (8.5 ml). Low volume and low concentration reagents are used. The sample treatment is rapid (less than 3 min per sample) and avoids the use of organic phase in the graphite furnace. The preconcentration factor used in this work was 14. The limit of detection and the limit of quantification in urine were, respectively, 0.27 and 0.9 μg l⁻¹. The relative standard deviation of aqueous standards (n=10) was 4% for a concentration of 100 μg l⁻¹ and 5% for a concentration of 400 μg l⁻¹. Recoveries from spiked urine with inorganic mercury, methyl-mercury, phenyl-mercury and diphenyl-mercury ranged from 86 to 98%.     

Comparative study between probe focussed sonication and conventional stirring in the evaluation of cadmium and copper in plants

Ultrasound (US)-assisted extraction has been widely used for metal ion extraction in plants due to its unique properties of decreased extraction time, minimal contamination, low reagent consumption and low cost. However, very few papers present a sound comparison between probe-focussed sonication and conventional stirring in the evaluation of metal ion extraction in plants. In this study, ultrasonic-assisted digestion has been evaluated and compared to magnetic stirring for total copper and cadmium determination by atomic absorption spectrometry in biological samples (plants, plankton and mussels). The same experimental conditions of sample amount and particle size, extractant solution and extraction time were applied for both ultrasound and magnetic stirring-assisted extraction methods in order to truly compare their effect on metal ion solubilisation. To gain further insight in this issue, dried and fresh plants were tested. The results obtained indicated that osmotic tension in cell walls, produced when dried and powdered samples were immersed in the extractant solution, had an important contribution to metal ion solubilisation, the enhancement due to US for the same purpose being negligible.     

On a differential problem coming from cell biology

Summary An initial and boundary value problem for a system of first order linear partial differential equations is studied. This problem arises in cell biology, when the evolution of a homogeneous cell population is modelled. Some existence, uniqueness and regularity results are proven; an estimate for the growth of the cell population is also obtained.This work was in part supported by the Istituto di Analisi Numerica of the C.N.R. in Pavia (Italy), the G.N.A.F.A. of the C.N.R. (Italy) and the Ministero della Pubblica Istruzione (Italy).