Jairo J. Pedrotti

Amperometric differential determination of ascorbic acid in beverages and vitamin C tablets using a flow cell containing an array of gold microelectrodes modified with palladium

A simple and attractive method for quantification of ascorbic acid (AA) in beers, soda, natural juices and commercial vitamin C tablets was achieved by combining flow injection analysis and amperometric detection. An array of gold microelectrodes electrochemically modified by deposition of palladium was employed as working electrode which was almost unaffected by fouling effects. Ascorbic acid was quantified in beverages and vitamin tablets using amperometric differential measurements. This method is based on three steps involving the flow injection of: (1) the sample plus a standard addition of AA, (2) the pure sample, and (3) the enzymatically-treated sample. The enzymatic treatment was carried out with Cucumis sativus tissue, which is a rich source of ascorbate oxidase, at pH 7. The calibration plots for freshly prepared ascorbic acid standards were very linear in the concentration range of 0.18–1.8 mg L−1 with a relative standard deviation (RSD) < 1%, while for real samples the deviations were between 2.7 % to 8.9 %.

Coconut-based plant tissue reactor for biosensing of catechol in flow injection analysis

Abstract A novel plant tissue biosensor is proposed in this paper. Catechol is determined by the reduction of its oxidation product on glassy carbon electrode after a biocatalytic conversion to quinone in an on-line coconut-based reactor by flow injection analysis. The remarkably high polyphenol oxidase activity of the tissue is successfully associated to its high stability and physical feasibility to manufacture the bioreactor. The sensor retains its enzyme activity for at least one week. Catechol can be determined at micromolar range in a rate of up to 60–90 samples per hour with good precision (RSD 2%). Optimization of the experimental parameters including bioreactor and cell design is addressed. An interference study is also included showing the limitations and other possibilities of the use for this plant material. Applicability to river water analysis and waste water is illustrated. Such use of biocatalytic material apart from the electrochemical detector still holds great advantages for easy screening of new material sources for biosensing applications.

An electrochemical flow-cell for permanent modification of graphite tube with palladium for mercury determination by electrothermal atomic absorption spectrometry

Abstract An electrochemical procedure for palladium deposition on the inner surface of pyrolytic graphite-coated tubes for permanent chemical modification and a cold vapor generation system for the pre-concentration and determination of mercury trace levels in rain, potable, and non-potable water and lake sediment by electrothermal atomic absorption spectrometry is proposed. A tubular electrochemical flow-cell was assembled on the original geometry of the graphite tube, which operated as the working electrode. A stainless steel tube, positioned downstream from the working electrode, was used as the auxiliary electrode. The applied potential was measured against a micro Ag/AgCl (sat) reference electrode inserted in the auxiliary electrode. Palladium solution in acetate buffer (100 mmol l −1 , pH=4.8), flowing at 0.5 ml min −1 for 60 min was used to perform the electrodeposition. A homemade cold vapor generation system composed of a peristaltic pump, an injector–commutator, a flow meter and a disposable polyethylene gas–liquid separator flask (approx. 4.0 ml volume) were used. Volumes of 1.0 ml of reagent (2.0% w/v NaBH 4 in 0.10 mol l −1 of NaOH) and 1.0 ml of reference or sample solution in 0.25 mol l −1 of HNO 3 were carried to the gas–liquid separator using the peristaltic pump. The mercury vapor was carried out to the modified graphite tube by argon flow (200 ml min −1 ), and pre-concentrated for 120 s. The characteristic mass for 1.0 ml of reference solution was 26 pg (R.S.D.=0.12%, n =5). The detection limit obtained was 93 pg ( n =20, 3δ). The reliability of the entire procedure was confirmed by addition and recovery tests and cold vapor atomic absorption spectrometry.

A fast, highly efficient, continuous degassing device and its application to oxygen removal in flow-injection analysis with amperometric detection

Abstract A new continuous degassing device, based on the permeation of gases dissolved in a liquid through the walls of a narrow-bore polymeric tube, is described. The key innovation, responsible for the superior efficiency in relation to other designs, consists in maintaining a reduced pressure of an inert gas (N2, ca. 1600 Pascal) in the degassing chamber that contains the coiled polymeric tube wandered by the solution. When applied to the continuous removal of oxygen from an electrolyte in flow-injection analysis, FIA, with amperometric detection (flow of 1.0 ml min , 34 s residence time), a decrease of at least 99.97% in the oxygen reduction current is experienced. Routine determination of 80 samples per hour of heavy metals like cadmium is afforded with a detection limit of about 10 ppb (1.8 × 10−12 mol of Cd(II) for 20-μl injections), by using a sessile drop mercury electrode. FIA with pre-concentration followed by voltammetric stripping extends the detection limit to the sub-ppb level, as illustrated by monitoring lead and cadmium in samples of drinking water.

A Batch Injection Analysis System for Ascorbic Acid Determination Using Amperometric Detection on a Sessile Mercury Drop Electrode

A batch injection analysis (BIA) system, which uses an automatic mercury electrode (AME) as an amperometric detector, is described. The capillary of this AME was adapted in an inverted position through the bottom of a simple cylindrical electrochemical cell, in order to generate more stable sessile drops and to grant free access for the tip of the programmable micropipettor. The BIA system was evaluated by using the electrochemical oxidation of L-ascorbic acid to dehydroascorbic acid on the sessile mercury drop electrode. Acetate buffer solution (50 mM, pH 4.8) was used as supporting electrolyte. The working electrode was operated at +0.230 V (vs. Ag/AgCl). The effect of the dispensing rate, of the dispensed volume, of the distance between the mercury drop and the pipettor tip, as well as of the solution level in the cell were evaluated. Injections of 50 µL were suitable to reach a detection limit of about 2.5 µM (450 ppb). At the 50 µM ascorbic acid level, an RSD of 1.6 % (N=35) was observed with or without mercury drop renewal between injections. A frequency of 300 injections per hour may be reached when the drop is renewed sporadically. The new BIA method was applied to the determination of ascorbic acid in packed/canned tropical fruit juices. Selectivity was granted by differential measurements of the peak current before and after exposure of samples to ascorbate oxidase (from cucumber).

Fast batch injection analysis of H2O2 using an array of Pt-modified gold microelectrodes obtained from split electronic chips

A fast and robust analytical method for amperometric determination of hydrogen peroxide (H(2)O(2)) based on batch injection analysis (BIA) on an array of gold microelectrodes modified with platinum is proposed. The gold microelectrode array (n=14) was obtained from electronic chips developed for surface mounted device technology (SMD), whose size offers advantages to adapt them in batch cells. The effect of the dispensing rate, volume injected, distance between the platinum microelectrodes and the pipette tip, as well as the volume of solution in the cell on the analytical response were evaluated. The method allows the H(2)O(2) amperometric determination in the concentration range from 0.8 μmolL(-1) to 100 μmolL(-1). The analytical frequency can attain 300 determinations per hour and the detection limit was estimated in 0.34 μmolL(-1) (3σ). The anodic current peaks obtained after a series of 23 successive injections of 50 μL of 25 μmolL(-1) H(2)O(2) showed an RSD<0.9%. To ensure the good selectivity to detect H(2)O(2), its determination was performed in a differential mode, with selective destruction of the H(2)O(2) with catalase in 10 mmolL(-1) phosphate buffer solution. Practical application of the analytical procedure involved H(2)O(2) determination in rainwater of São Paulo City. A comparison of the results obtained by the proposed amperometric method with another one which combines flow injection analysis (FIA) with spectrophotometric detection showed good agreement.

Flow-through Cell Based on an Array of Gold Microelectrodes Obtained From Modified Integrated Circuit Chips

The construction of a flow-through cell incorporating an array of gold microelectrodes is described and its application to flow injection analysis with amperometric detection is presented. Simple modification of almost any conventional integrated circuit chip, used as an inexpensive source of pre-assembled gold micro-wires, leads to the rapid and successful preparation of arrays of 8–48 elements. The polymeric encapsulation material from the top face of the chip is removed by abrasion until the gold micro-wires (used to interconnect the silicon circuit to the external contact pins of the chip) are disrupted and their transversal (elliptical) sections become exposed. Once polished, the flat and smooth top surface of the gold microelectrode-array chip (MEAC) is provided with a spacer and fitted under pressure against an acrylic block with the reference and auxiliary electrodes, to form the electrochemical (thin-layer) flow cell, while the contact pins are plugged into a standard IC socket. This design ensures autonomous electric contact with each electrode and allows fast dismantling for polishing or substitution. The performance of flow cells with MEACs was investigated utilizing the technique of reverse pulse amperometry without oxygen removal. A method was established for the determination of the copper concentration in sugar cane spirit, regulated by law for beverages. Samples from industrial producers and small-scale (alembic) brewers were compared. With a 24 MEAC, a detection limit of 30 µg l -1 of copper (4.7 × 10 -7 mol l -1 of Cu II for 100 µl injections) was calculated. Routine operation was established at a frequency of 60–90 determinations per hour. Intercomparison with atomic absorption spectrometric determinations resulted in excellent agreement.

Flow injection analysis of ethyl xanthate by gas diffusion and UV detection as CS2 for process monitoring of sulfide ore flotation

A sensitive and robust analytical method for spectrophotometric determination of ethyl xanthate, CH(3)CH(2)OCS(2)(-) at trace concentrations in pulp solutions from froth flotation process is proposed. The analytical method is based on the decomposition of ethyl xanthate, EtX(-), with 2.0 mol L(-1) HCl generating ethanol and carbon disulfide, CS(2). A gas diffusion cell assures that only the volatile compounds diffuse through a PTFE membrane towards an acceptor stream of deionized water, thus avoiding the interferences of non-volatile compounds and suspended particles. The CS(2) is selectively detected by UV absorbance at 206 nm (epsilon=65,000 L mol(-1) cm(-1)). The measured absorbance is directly proportional to EtX(-) concentration present in the sample solutions. The Beers law is obeyed in a 1x10(-6) to 2x10(-4) mol L(-1) concentration range of ethyl xanthate in the pulp with an excellent correlation coefficient (r=0.999) and a detection limit of 3.1x10(-7) mol L(-1), corresponding to 38 microg L(-1). At flow rates of 200 microL min(-1) of the donor stream and 100 microL min(-1) of the acceptor channel a sampling rate of 15 injections per hour could be achieved with RSD<2.3% (n=10, 300 microL injections of 1x10(-5) mol L(-1) EtX(-)). Two practical applications demonstrate the versatility of the FIA method: (i) evaluation the free EtX(-) concentration during a laboratory study of the EtX(-) adsorption capacity on pulverized sulfide ore (pyrite) and (ii) monitoring of EtX(-) at different stages (from starting load to washing effluents) of a flotation pilot plant processing a Cu-Zn sulfide ore.

Flow injection analysis of ethyl xanthate by in-line dialysis and UV spectrophotometric detection

A simple and sensitive spectrophotometric flow method for determination of low concentrations of the flotation collector O-ethyldithiocarbonate (ethyl xanthate, CH(3)CH(2)-O-CS(2)(-)) in solutions is described. The method is based on ethyl xanthate detection at 301nm in medium of NaOH 50mmolL(-1). By injection of 200muL of sample, the analytical method shows linear response for the ethyl xanthate concentration from 0.5 up to 500mumolL(-1). Successive injections of 4mumolL(-1) ethyl xanthate (n=23) show a coefficient of variation lower than 0.6%, denoting high repeatability. The detection limit is 0.3mumolL(-1). At a flow rate of 2.0mLmin(-1), a frequency of 120injections/h of ethyl xanthate can be attained. By introduction of a tangential dialysis cell in the FIA system, the manual sample filtration step with 0.22mum filter was eliminated and the residual interference of suspended material, was completely overcome even for unfiltered sludge suspension samples, an important advantage that compensates for the frequency reduction to 25injections/h elevation and detection limit elevation to 2mumolL(-1), still outreaching for many applications. Potential applications of the method embrace the at line determination of ethyl xanthate in the ore processing industry, control of the concentration at its optimal level during the flotation process, as well as monitoring of residues in the effluents.

Ultra-simple adaptor to convert batch cells with mercury drop electrodes in voltammetric detectors for flow analysis

A simple, robust and fast-responding flow adaptor for mercury drop electrodes (MDEs) is described. An L-shaped PTFE tube with an internal diameter of 0.5 mm is fixed with a silicone ring on the glass capillary of a MDE, in such a way as to direct the outcoming flow onto the mercury drop, from a distance of about 0.5 mm. Any commercial or laboratory-made batch cell, provided with an MDE, serves for the purpose. The level of supporting electrolyte in the cell is maintained constant through a siphon or a lateral draining orifice. The adaptor is compatible with all the different brands and operating modes of the MDEs (free dropping, controlled drop time, renewable static drop, hanging drop or sessile drop). Flow injection experiments were conducted with the following amperometric detection modes: sampled-DC, reverse pulse amperometry (RPA), and anodic stripping voltammetry (ASV). The FIA-RPA peaks presented a R.S.D.<0.8% for 1.0x10(-5) mol l(-1) lead(II) (N=30, V(sample)=100 mul). The response time (0-63% of the signal maximum) to a concentration step is 1.2 s for 500 mul injections of 0.1 mmol l(-1) ascorbic acid in acetate buffer at a flow rate of 1 ml min(-1), which corresponds to a response volume of 20 mul. As an example of practical application, copper(II) was determined in fertilizers by RPA using the standard addition method, at an analytical frequency of 90 injections per h.