Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

Resonant Wave Interactions in the Equatorial Waveguide

Weakly nonlinear interactions among equatorial waves have been explored in this paper using the adiabatic version of the equatorial beta-plane primitive equations in isobaric coordinates. Assuming rigid lid vertical boundary conditions, the conditions imposed at the surface and at the top of the troposphere were expanded in a Taylor series around two isobaric surfaces in an approach similar to that used in the theory of surface-gravity waves in deep water and capillary-gravity waves. By adopting the asymptotic method of multiple time scales, the equatorial Rossby, mixed Rossby-gravity, inertio-gravity, and Kelvin waves, as well as their vertical structures, were obtained as leading-order solutions. These waves were shown to interact resonantly in a triad configuration at the O(epsilon) approximation. The resonant triads whose wave components satisfy a resonance condition for their vertical structures were found to have the most significant interactions, although this condition is not excluding, unlike the resonant conditions for the zonal wavenumbers and meridional modes. Thus, the analysis has focused on such resonant triads. In general, it was found that for these resonant triads satisfying the resonance condition in the vertical direction, the wave with the highest absolute frequency always acts as an energy source (or sink) for the remaining triad components, as usually occurs in several other physical problems in fluid dynamics. In addition, the zonally symmetric geostrophic modes act as catalyst modes for the energy exchanges between two dispersive waves in a resonant triad. The integration of the reduced asymptotic equations for a single resonant triad shows that, for the initial mode amplitudes characterizing realistic magnitudes of atmospheric flow perturbations, the modes in general exchange energy on low-frequency (intraseasonal and/or even longer) time scales, with the interaction period being dependent upon the initial mode amplitudes. Potential future applications of the present theory to the real atmosphere with the inclusion of diabatic forcing, dissipation, and a more realistic background state are also discussed.

SURFACE ALFVEN WAVE DAMPING IN A THREE-DIMENSIONAL SIMULATION OF THE SOLAR WIND

Here we investigate the contribution of surface Alfven wave damping to the heating of the solar wind in minima conditions. These waves are present in the regions of strong inhomogeneities in density or magnetic field (e.g., the border between open and closed magnetic field lines). Using a three-dimensional (3D) magnetohydrodynamics (MHD) model, we calculate the surface Alfven wave damping contribution between 1 and 4 R(circle dot) (solar radii), the region of interest for both acceleration and coronal heating. We consider waves with frequencies lower than those that are damped in the chromosphere and on the order of those dominating the heliosphere: 3 x 10(-6) to 10(-1) Hz. In the region between open and closed field lines, within a few R(circle dot) of the surface, no other major source of damping has been suggested for the low frequency waves we consider here. This work is the first to study surface Alfven waves in a 3D environment without assuming a priori a geometry of field lines or magnetic and density profiles. We demonstrate that projection effects from the plane of the sky to 3D are significant in the calculation of field line expansion. We determine that waves with frequencies >2.8 x 10(-4) Hz are damped between 1 and 4 R(circle dot). In quiet-Sun regions, surface Alfven waves are damped at further distances compared to active regions, thus carrying additional wave energy into the corona. We compare the surface Alfven wave contribution to the heating by a variable polytropic index and find it as an order of magnitude larger than needed for quiet-Sun regions. For active regions, the contribution to the heating is 20%. As it has been argued that a variable gamma acts as turbulence, our results indicate that surface Alfven wave damping is comparable to turbulence in the lower corona. This damping mechanism should be included self-consistently as an energy driver for the wind in global MHD models.