Ion-exchange voltammetry with nafion/poly(sodium 4-styrenesulfonate) mixed coatings on mercury film electrodes: characterization studies and application to the determination of trace metals

This work aimed to produce improved polymer coatings for the modification of thin mercury film electrodes (TMFEs). The goal is to obtain sensitive, reproducible, mechanically stable and antifouling devices suitable for the determination of trace metal cations in complex media. Therefore, novel mixed coatings of two sulfonated cation-exchange polymers of dissimilar characteristics-Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS)-were produced by solvent evaporation onto glassy carbon electrodes. The effect of the mass ratio (NA:PSS) on the film morphology was studied by scanning electron microscopy, revealing the formation of biphasic polymer systems, where PSS bead-shaped clusters appeared randomly dispersed into a uniform and compact NA environment. The permselectivity/ion-exchange features of the mixed films onto glassy carbon were evaluated using cathecol, urate, and dopamine. To allow trace metal analysis, thin mercury films were plated through the NA/PSS coatings, being the reproducibility and ion-exchange features of the mixed coatings-TMFE evaluated using lead ions. The best NA/PSS coating was found for the mass ratio of 5.3. Analytical performance of the NA/PSS-TMFE yielded a detection limit of 5.5 nM (3sigma), and the application of this modified electrode to an untreated polluted estuarine water sample produced significant improvements in the quality of the signal compared with that for a bare TMFE.     

Mixed polyelectrolyte coatings on glassy carbon electrodes: Ion-exchange, permselectivity properties and analytical application of poly-l-lysine-poly(sodium 4-styrenesulfonate)-coated mercury film electrodes for the detection of trace metals

The present work describes the preparation, optimization and characterization of mixed polyelectrolyte coatings of poly-l-lysine (PLL) and poly(sodium 4-styrenesulfonate) (PSS) for the modification of thin mercury film electrodes (MFEs). The novel-modified electrodes were applied in the direct analysis of trace metals in estuarine waters by square-wave anodic stripping voltammetry (SWASV). The effects of the coating morphology and thickness and also of the monomeric molar ratio PLL/PSS on the cation-exchange ability of the PLL–PSS polyelectrolyte coatings onto glassy carbon (GC) were evaluated using target cationic species such as dopamine (DA) or lead cation. Further, the semi-permeability of the PLL–PSS-coated electrodes based both on electrostatic interactions and on molecular size leads to an improved anti-fouling ability against several tensioactive species. The analytical usefulness of the PLL–PSS-mixed polyelectrolyte coatings on thin mercury film electrodes is demonstrated via SWASV measurements of trace metals (lead, copper and cadmium at the low nanomolar level; accumulation time of 180 s) in estuarine waters containing moderate levels of dissolved organic matter, resulting in a fast and direct methodology requiring no sample pretreatment.     

Nafion-coated bismuth film and nafion-coated mercury film electrodes for anodic stripping voltammetry combined on-line with ICP-mass spectrometry

Nafion-coated bismuth film electrodes (NCBFEs) and Nafion-coated mercury film electrodes (NCMFEs) were used to electrochemically preconcentrate metal analytes for subsequent analysis by inductively coupled plasma-mass spectrometry (ICP-MS). Either type of electrodes is part of a thin-layer electrochemical flow cell that is positioned upstream of a microconcentric nebulizer for the ICP-MS. Performances of these electrodes were compared in terms of the analytical "figures of merit" (e.g., dynamic ranges, reproducibility, hydrodynamic stability, and elimination of matrix effects detrimental to ICP-MS). The coupled technique (ASV-ICP-MS) is found to possess a wide dynamic range (at least 4 to 5 orders of magnitude) and to be reproducible. Both electrodes are much more stable than the thin mercury film electrode (TMFE) traditionally used for ASV-ICP-MS, with the lifetime of the NCBFE exceeding 8 h. Adopting these electrodes for ASV-ICP-MS overcomes the problems associated with a TMFE, the erosion of which decreases the sample throughput, affects the analysis precision, and contaminates conventional glass nebulizers and spray chambers of the spectrometer. The medium exchange procedure inherent in ASV is successfully implemented with a two-valve flow injection system for the accumulation of trace Cd2+ into the electrode from a certified seawater sample, followed by stripping Cd into a solution that is compatible to the ICP-MS operation.     

The use of Nafion-coated thin mercury film electrodes for the determination of the dissolved copper speciation in estuarine water

Differential pulse anodic stripping voltammetry (DPASV) using a Nafion-coated thin mercury film electrode (NCTMFE) was implemented to determine the dissolved copper speciation in saline estuarine waters containing high concentrations of dissolved organic matter (DOM). The study used model ligands and estuarine water from San Francisco Bay, California, USA to demonstrate that the NCTMFE is more effective at distinguishing between electrochemically inert and labile copper species when compared to the conventional thin mercury film electrode (TMFE). Copper titration results verify that the NCTMFE better deals with high concentrations of DOM by creating a size-exclusion barrier that prevents DOM from interacting with the mercury electrode when performing copper speciation measurements. Pseudovoltammograms were used to illustrate that copper complexes found in natural waters were more apt to be electrochemically inert at the NCTMFE relative to the TMFE when subjected to high negative overpotentials. Copper speciation results using the NCTMFE from samples collected in San Francisco Bay estimated that >99.9% of all copper was bound to strong copper-binding ligands. These L₁-class ligands exceeded the concentration of total dissolved copper in all samples tested and control the equilibrium of ambient [Cu²⁺] in the San Francisco Bay estuary.     

Poly(ester sulphonic acid) coated mercury thin film electrodes: characterization and application in batch injection analysis stripping voltammetry of heavy metal ions

Mercury-thin film electrodes coated with a thin film of poly(ester sulphonic acid) (PESA) have been investigated for application in the analysis of trace heavy metals by square wave anodic stripping voltammetry using the batch injection analysis (BIA) technique. Different polymer dispersion concentrations in water/acetone mixed solvent are investigated and are characterised by electrochemical impedance measurements on glassy carbon and on mercury film electrodes. The influence of electrolyte anion, acetate or nitrate, on polymer film properties is demonstrated, acetate buffer being shown to be preferable for stripping voltammetry applications. Although stripping currents are between 30 and 70% less at the coated than at bare mercury thin film electrodes, the influence of model surfactants on stripping response is shown to be very small. The effect of the composition of the modifier film dispersion on calibration plots is shown; however, detection limits of around 5 nM are found for all modified electrodes tested. This coated electrode is an alternative to Nafion-coated mercury thin film electrodes for the analysis of trace metals in complex matrices, particularly useful when there is a high concentration of non-ionic detergents.     

A study of Nafion-coated bismuth-film electrodes for the determination of trace metals by anodic stripping voltammetry

This work reports on the fabrication, characterization and applications of Nafion-coated bismuth-film electrodes (NCBFE's) for the determination of trace metals by anodic stripping voltammetry (ASV). A NCBFE was typically prepared by first applying a 5 microl drop of a 1% Nafion solution onto the surface of a glassy-carbon rotating-disk electrode. After evaporation of the solvent, the Bi film was plated on the electrode in situ(i.e. by spiking the sample with 1000 microg l(-1) of Bi(iii) and simultaneous electrolytic deposition of the metal ions and bismuth film on the electrode surface at -1.4 V) or ex-situ(i.e. by electrolytic deposition of the bismuth film in a separate solution containing 1000 microg l(-1) of Bi(iii), followed by the ASV measurement step in the sample solution). Various fabrication and operational parameters were thoroughly investigated and discussed in terms of their effect on the ASV signals. It was found that this voltammetric sensor was suitable for the determination of metals at trace levels by square-wave ASV (SWASV) due to its multi-element detection potential, improved analytical sensitivity, high resistance to surfactants, low cost, ease of fabrication, robustness, speed of analysis and low toxicity (as compared to traditional mercury electrodes). In the presence of 4 mg l(-1) of Triton X-100, the NCBFE afforded a 10-fold peak height enhancement for the Pb peak and a 14-fold enhancement for the Cd peak over a bare BFE while the determination of Zn was feasible only on the NCBFE. The limits of detection (at a signal-to-noise ratio of 3) were 0.1 microg l(-1) for Cd and Pb and 0.4 microg l(-1) for Zn for a deposition time of 10 min. Finally, the electrode was applied to different real samples (tap-water, urine and wine) for the analysis of trace metals with satisfactory results.     

Validation of bismuth film electrode for determination of cobalt and cadmium in soil extracts using ICP-MS

A study is presented on the use of the bismuth film electrode (BiFE) operated in the anodic stripping and the cathodic adsorptive stripping voltammetry (ASV, CAdSV) modes, for the determination of two trace heavy metals (Cd and Co, respectively), in soil extract samples. Two types of BiFE were examined in this study: the in situ prepared BiFE, which was employed in ASV determination of Cd, and the ex situ prepared BiFE, which was used in CAdSV of Co with dimethylglyoxime (DMG) as complexing agent. A series of unpretreated soil extracts with varying Cd and Co concentrations were analyzed, and the results obtained compared to those determined using inductively coupled plasma-mass spectrometry (ICP-MS). The results revealed the suitability of stripping analysis at the BiFE for determination of μg l⁻¹ levels of heavy metals in soil extracts. The promising results obtained here, coupled with the non-toxic nature of bismuth (in comparison to commonly used mercury electrodes employed in stripping analysis), offer great promise in centralized and decentralized analysis of trace heavy metals in complex environmental matrices.     

Perfluorinated anion-exchange polymer mercury film electrode for anodic stripping voltammetric determination of zinc(II): effect of model organic compounds

The determination of zinc ion (1-60 ng ml⁻¹) by anodic square-wave stripping voltammetry on an anion-exchange perfluorinated polymer Tosflex mercury film electrodes (TMFE) was evaluated. The detection limit was 0.1 ng ml⁻¹ Zn(II). The effect of various organic compounds (gelatin, albumin, starch, camphor, humic acid, Triton X-100, sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB)) is explored. The results indicate that due to the size-exclusion and ion-exchange properties of Tosflex film, the TMFE is considerably more resistant to organic interference than the bare mercury film electrode.     

Electrochemical measurement of mercury concentration profiles in the pore-waters of sediments of the Venice Lagoon by ion-exchange voltammetry at polymer modified electrodes

Glassy carbon electrodes modified with coatings of poly-[1-methyl-3-(pyrrol-1-ylmethyl)pyridinium], poly-MPP, were employed for preconcentrating and detecting the anionic complex HgCl4(2-), which is the prevailing inorganic Hg(II) species in salt waters such as the pore-waters of sediments here examined. The application of ion-exchange voltammetry at poly-MPP coated electrodes in combination with an in situ pore-water sampler allowed the measurement of concentration vs. depth profiles for mercury dissolved in the pore-waters of a salt-marsh and of a mud-flat located in a polluted area of the Venice Lagoon. The trends of the mercury profiles are discussed in comparison with the trends measured from the same location for other trace metals (Zn, Cd, Cu and Pb) and reduced species such as S(-II) and Fe(II).     

Redox magnetohydrodynamic enhancement of stripping voltammetry: toward portable analysis using disposable electrodes, permanent magnets, and small volumes

The use of redox magnetohydrodynamics (MHD) to enhance the anodic stripping voltammetry (ASV) response of heavy metals has been investigated, with respect to achieving portability: disposable electrodes consisting of screen-printed carbon (SPC) on a low temperature co-fired ceramic (LTCC) substrate, small volumes, and permanent magnets. The analytes tested (Cd(2+), Cu(2+), and Pb(2+)) were codeposited on SPC with Hg(2+) to form a Hg thin film electrode. High concentrations of Fe(3+) were used to produce a high cathodic current which generates a significant Lorentz force in the presence of a magnetic field. This Lorentz force induces solution convection during the deposition step, enhancing the mass transport of analytes to the electrode and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared to analyses performed without a magnet. The effects on ASV signal of varying Hg(2+) concentration (0.10 and 1.0 mM), deposition time (10-600 s), and electrode surface roughness were investigated. In addition, analyses were performed using a real lake water matrix. By using the disposable LTCC-SPC working electrodes in small volumes (150 microL) and with small permanent magnets (0.78 T), peak areas were increased by 75% when compared to the signal obtained in the absence of a magnetic field. A limit of detection of 25 nM for Cd(2+) was observed with only a 1 min preconcentration time.     

Functioning of antimony film electrode in acid media under cyclic and anodic stripping voltammetry conditions

New insights into the functioning, i.e. electrochemical behaviour and analytical performance, of in situ prepared antimony film electrodes (SbFEs) under square-wave anodic stripping (SW-ASV) and cyclic (CV) voltammetry conditions are presented by studying several key operational parameters using Pb(II), Cd(II) and Zn(II) as model analyte ions. Five different carbon- and metal-based substrate transducer electrodes revealed a clear advantage of the former ones while the concentration of the precursor Sb(III) ion exhibited a distinct influence on the ASV functioning of the SbFE. Among six acids examined as potential supporting electrolytes the HNO₃ was demonstrated to yield nearly identical results in conducting ASV experiments with SbFE as so far almost exclusively used HCl. This is extremely important as HNO₃ is commonly employed acidifying agent in trace metal analysis, especially in elemental mass spectrometry measurements. By carrying out a systematic CV and ASV investigation using a medium exchange protocol, we confirmed the formation of poorly soluble oxidized Sb species at the substrate electrode surface at the end of each stripping step, i.e. at the potentials beyond the anodic dissolution of the antimony film. Hence, the significance of the cleaning and initializing the surface of a substrate electrode after accomplishing a stripping step was thoroughly studied in order to find conditions for a complete removal of the adhered Sb-oxides and thus to assure a memory-free functioning of the in situ prepared SbFE. Finally, the practical analytical application of the proposed ASV method was successfully tested and evaluated by measuring the three metal analytes in ground (tap) and surface (river) water samples acidified with HNO₃. Our results approved the appropriateness of the SbFE and the proposed method for measuring low μg L⁻¹ levels of some toxic metals, particularly taking into account the possibility of on-field testing and the use of low cost instrumentation.     

Comparison of physicochemical speciation procedures with metal toxicity to chlorella pyrenoidosa

Metal speciation as measured by anodic stripping voltammetry (ASV), adsorption on a resin with adsorbed hydrated aluminium oxide, and dialysis with receiving resins is compared with the toxicity of the metals to the freshwater green alga Chlorella pyrenoidosa Chick. In the presence of natural and synthetic ligands, similar labile fractions of metals were obtained for ASV at three electrodes (hanging mercury drop electrode, mercury film electrode and Nafion-coated mercury film electrode). The toxic fractions determined by ASV and bioassay were in reasonable agreement for zinc, cadmium and copper, and alteration of the analytical conditions provided some measure of agreement for lead. The resin with adsorbed hydrated aluminium oxide correlated well with bioassay for copper, but over-estimated lead toxicity and under-estimated cadmium toxicity. Dialysis with receiving resins under-estimated metal bioaccumulation in the presence of ligands. Metal speciation analysis for water samples gave higher toxic fractions for metals in samples of polluted river water and road runoff samples than those found in pristine river water.     

Assembly of poly(N-isopropylacrylamide)-co-acrylic acid microgel thin films on polyelectrolyte multilayers: Effects of polyelectrolyte layer thickness, surface charge, and microgel solution pH

Temperature- and pH-sensitive poly(N-isopropylacrylamide)?Cco-acrylic acid (pNIPAm-co-AAc) microgels were deposited on glass substrates coated with polyelectrolyte multilayers composed of the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(sodium 4-styrenesulfonate) (PSS). The microgel density and structure of the resultant films were investigated as a function of: (1) the number of PAH/PSS layers (layer thickness); (2) the charge on the outer layer of the polyelectrolyte multilayer film; and (3) the pH of microgel deposition solution. The resultant films were studied by differential interference contrast optical microscopy, atomic force microscopy, and scanning electron microscopy. It was found that the coverage of the microgels on the surface was a complex function of the pH of the deposition solution, the charge on the outer layer of the polyelectrolyte thin film and the PAH/PSS layer thickness; although it appears that microgel charge plays the biggest role in determining the resultant surface coverage.     

Determination of Aluminum by Adsorptive Cathodic Stripping Voltammetry with 1,2‐Dihydroxyanthraquinone‐3‐Sulfonic Acid (DASA): Effect of Thin Mercury Film Electrode

An analytical technique for aluminum (Al) based upon the complexation reaction between Al and the ligand – DASA (1,2‐dihydroxy‐anthraquinone‐3‐sulfonic acid) has previously been implemented successfully at the hanging mercury drop electrode (HMDE). There are several advantages of using mercury film electrodes (TMFE) over the HMDE, particularly if disposal of mercury is of concern. The novelty of using TMFE for adsorptive cathodic stripping voltammetry (ACSV) of Al – DASA is demonstrated in this paper. The peak potential used for the detection of Al in this system was at ?1.15 V (vs. Ag/AgCl). The method produced a limit of detection (LOD) of 1 μM (n=5) and a linear working range of 1–20 μM Al. Atomic force microscopy methods were used to investigate the nature of the TMFE and its interaction with DASA. The mercury droplets on the TMFE have a limited volume and this may lead to overloading of the electrode at relatively low concentrations of DASA. Interferences from Fe, Ca, Zn and Mg were investigated with only Fe appearing to interfere with the Al‐DASA system. Two masking agents (o‐phenanthroline and 2,2′‐bipyridyl) were shown to be effective at preventing the Fe interference.     

Polymer-Mercury Coated Screen-Printed Sensors for Electrochemical Stripping Analysis of Heavy Metals

In the perspective of in-field stripping analysis of heavy metals, the use and disposal of toxic mercury solutions (necessary to plate a mercury film on a carbon electrode surface) presents a problem. The aim of this work was the development of mercury coated screen-printed electrodes previously prepared in the lab and ready to use in-field. Thus some commercially available polymers like Nafion®, Eastman Kodak AQ29®, and Methocel® were investigated as mercury entrapping systems for electrochemical stripping analysis of heavy metals. Screen-printed disposable cells with a silver pseudo-reference electrode, a graphite counter electrode, and a graphite working electrode were used. To modify the sensor, the polymer solution was cast onto the carbon working electrode surface. Detection limits of 0.8 and 1 μg/L were obtained for lead and cadmium respectively. Since Methocel® based electrodes showed the best performance, they were used for the analysis of real samples. The results were compared with those obtained using a classical thin mercury film electrode and ICP spectroscopy.

All the experiments reported here were performed in un-deareated solutions as required for in-field analysis.     

Iridium Oxide Film Electrodes for Anodic Stripping Voltammetry

The new iridium oxide film electrode, applied for the determination of lead(II), cadmium(II) and copper(II) traces using differential pulse anodic stripping voltammetry (DP ASV) is presented. The electrode display an interesting stripping voltammetric performance which compares with electrodes commonly used in voltammetry. The deposited film is known as anodically electrodeposited iridium oxide film (AEIROF). The AEIROF electrode is characterized by long‐term stability (more than 40 days) and very good reproducibility of the analytical signals in this time (≤12% for 0.5 μM of lead). The regeneration of iridium film is very simple in a time shorter than 60 seconds. The effects of various factors such as: thickness of AEIROF film, preconcentration potential and time, supporting electrolyte composition, potential interferences are optimized. The detection limit for AEIROF film electrode based on glassy carbon for an accumulation time of 30 s is as low as 7 nM for lead(II). The repeatability of the method at a concentration level of the lead(II) as low as 0.5 μM, expressed as RSD is 2.5% (n=10). The proposed method was successfully applied and validated by studying certified reference material CTA‐OTL‐1. Such an attractive use of ‘mercury–free’ ‐ environmentally friendly electrodes offers great promise to measure trace metals.     

Nafion-coated mercury thin film electrodes for batch-injection analysis with anodic stripping voltammetry

Batch-injection analysis exhibits the advantages of rapid and simple electroanalysis of microlitre samples. Nafion-coated mercury thin film electrodes have been evaluated for use in batch-injection analysis with anodic stripping voltammetry (BIA-ASV). The advantages of Nafion-coated electrodes in reducing electrode contamination by components of complex matrices are combined with the analysis of small microlitre sample volumes. The measurement of traces of lead and cadmium is used to illustrate the approach. An optimised procedure for formation of Nafion-coated mercury thin film electrodes is evolved. The relative sensitivity for BIA-ASV at electrodes with and without Nafion coatings is 0.9 and 0.8 for cadmium and lead respectively; detection limits are 2 x 10(-9) M and 4 x 10(-9) M. Studies were done concerning the influence of surfactants and their effect was found to be much less with the Nafion film coating. Applications to real environmental samples are demonstrated.     

Nafion/Poly(sodium 4‐styrenesulfonate) Mixed Coating Modified Bismuth Film Electrode for the Determination of Trace Metals by Anodic Stripping Voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation‐exchange polymers, Nafion (NA) and poly(sodium 4‐styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA‐PSS/BiFE). The characteristics of GC/NA‐PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltammetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L^?1 for Cd(II) and 93 ng L^?1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA‐PSS/BiFE can be a reproducible and robust tool for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface‐active compounds.     

A stannum-bismuth composite film electrode for simultaneous determination of zinc(II) and cadmium(II) using differential pulse anodic stripping voltammetry

The development and use of 'green' electrode materials is extremely attractive for the routine use of disposable metal sensors. Bismuth is an environmentally-friendly element and a bismuth film electrode was proposed as an alternative to mercury film electrodes. Compared with bismuth, stannum is a more 'environmentally friendly' material. The stannum-bismuth composite film electrode prepared by the in situ electrodeposition of stannum and bismuth on the glassy carbon substrate is reported for the first time. Compared with bismuth film and stannum film electrodes, the stannum-bismuth composite film electrode revealed better electroanalytical performance, and can be used as a possible alternative electrode for electrochemical stripping analysis of trace heavy metals.     

Optimisation of mercury film deposition on glassy carbon electrodes: evaluation of the combined effects of pH, thiocyanate ion and deposition potential

The combined effects of pH, thiocyanate ion and deposition potential in the characteristics of thin mercury film electrodes plated on glassy carbon surfaces are evaluated. Charges of deposited mercury are used as an experimental parameter for the estimation of the effectiveness of the mercury deposition procedure. The sensitivity of the anodic stripping voltammetry (ASV) method for the determination of lead at in situ and at ex situ formed thin mercury films are also examined. It was concluded that, in acidic solutions (pH 2.5-5.7) and fairly negative deposition potentials, e.g. −1.3 to −1.5 V, thiocyanate ion promotes the formation of the mercury film, in respect both to the amount of deposited mercury and to the mercury deposition rate. Also, the mercury coatings produced in thiocyanate solutions are more homogeneous, as depicted by microscopic examinations. In the presence of thiocyanate there is no obvious advantage of using high concentrations of mercury and/or high deposition times for the in situ and ex situ preparation of the mercury film electrodes. The optimised thin mercury film electrode ex situ prepared in a 5.0 mM thiocyanate solution of pH 3.4 was successfully applied to the ASV determination of lead and copper in acidified seawater (pH 2). The limit of detection (3σ) was 6×10⁻¹¹ M for lead and 2×10⁻¹⁰ M for copper for a deposition time of 5 min. Relative standard deviations (R.S.D.s) of <1.2% were obtained for determinations at the nanomolar of concentration level.