Heavy metals and health risk assessment of Brazilian artisanal cheeses.

Dairy products stand out as a food matrix susceptible to the contamination of heavy metals via cattle feed and environmental or processing conditions. Specifically, in the case of cheese, the concentrations can be further increased depending on the production process. The artisanal cheese market has been standing out, especially in Brazil, due to cultural and gastronomic reasons. Eight types of Brazilian artisanal cheese were analyzed for metal concentrations (chromium, copper, cadmium, lead, arsenic, and mercury, n = 80, 10 samples of each cheese) using inductively coupled plasma mass spectrometry. Based on the results, a health risk assessment was carried out, based on the determination of estimated daily intake, target hazard quotient (THQ), and hazard index (HI). Variable concentrations were observed between the types of cheese, but in all cases the THQ and HI values were less than 1, indicating an absence of potential risk in the consumption of artisanal cheeses in relation to the intake of heavy metals.

Cocktail effects of emerging contaminants on zebrafish: Nanoplastics and the pharmaceutical diphenhydramine.

Nanoplastics (NPLs) became ubiquitous in the environment, from the air we breathe to the food we eat. One of the main concerns about the NPLs risks is their role as carrier of other environmental contaminants, potentially increasing their uptake, bioaccumulation and toxicity to the organisms. Therefore, the main aim of this study was to understand how the presence of polystyrene NPLs (∅ 44 nm) will influence the toxicity (synergism, additivity or antagonism) of the antihistamine diphenhydramine (DPH), towards zebrafish (Danio rerio) embryos, when in dual mixtures. After 96 hours (h) exposure, at the organismal level, NPLs (0.015 or 1.5 mg/L) + DPH (10 mg/L) induced embryo mortality (90%) and malformations (100%) and decreased hatching (80%) and heartbeat rates (60%). After 120 h exposure, NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L) decreased larvae swimming distance (30-40%). At the biochemical level, increased glutathione S-transferases (55-122%) and cholinesterase (182-343%) activities were found after 96 h exposure to NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L). However, catalase (CAT) activity remained similar to the control group in the mixtures, inhibiting the effects detected after the exposure to 1.5 mg/L NPLs alone (increased 230% of CAT activity). In general, the effects of dual combination - NPLs + DPH (even at concentrations as low as 10 µg/L of DPH) - were more harmful than the correspondent individual exposures, showing the synergistic interactions of the dual mixture and answering to the main question of this work. The obtained results, namely the altered toxicity patterns of NPLs + DPH compared with the individual exposures, show the importance of an environmental risk assessment considering NPLs as a co-contaminant due to the potential NPLs role as vector for other contaminants.

Recovery of palladium from a low grade palladium solution by anionic-ion exchange: kinetics, equilibrium, and metal competition.

Petroleum spent catalysts may contain a significant amount of palladium (Pd) together with other major [aluminum (Al), nickel (Ni), and molybdenum (Mo)] and minor [iron (Fe), lead (Pb), and vanadium (V)] elements. Due to the high intrinsic value of Pd and its scarcity in natural ores, its recovery is highly desired. For this purpose, the ability of a strong basic anionic- resin, Purogold™ A194 resin, to remove Pd from the solution was assessed. Data from kinetic and equilibrium studies, performed under batch mode in 1 mol/L of NaCl and 1 mol/L of HNO3 at (21 ± 1) °C, revealed that the removal of Pd fits well a pseudo-second-order kinetic model [constant rate value, k2, of (0.062 ± 0.010) g/(mmol.min)] and a Langmuir isotherm [maximum sorption capacity of (0.80 ± 0.02) mmol/g with an affinity of resin binding sites towards Pd, KL, of (0.18 ± 0.02) L/mmol], respectively. The sorption of other metals (Al, Fe, Pb, Mo, Ni, and V) that may be present in spent catalyst leachates was tested under similar experimental conditions [CM = 2.5 mmol/L, 1 mol/L of NaCl and 1 mol/L of HNO3 at (21 ± 1) °C)] and the resin showed little affinity towards each one of these metals. Also, simultaneous multi-element batch experiments with Pd and the major components (M = Al, Ni, and Mo ions) ([M]/[Pd] molar ratios between 3.4 and 52 were used) pointed out that the resin is highly selective towards Pd suggesting that the resin can be used in the selective recovery of Pd from petroleum spent catalyst leachates.

Assessment of diphenhydramine toxicity - Is its mode of action conserved between human and zebrafish?

The main aim of the study is to evaluate the effects of the pharmaceutical diphenhydramine (DPH) on embryo-larvae Danio rerio across distinct levels of organization - individual and subcellular - and correlate those effects with the DPH mode of action (MoA) assessed by in silico analysis. An embryos heartbeat rate reduction was observed at 10 mg/L DPH, but 0.001 to 10 mg/L did not significantly affect the zebrafish survival, hatching and morphology. Larvae swimming distance decreased (hypoactivity) at 1 and 10 mg/L DPH. Moreover, the straightforward movements decrease and the increase in the zigzag movements or movements with direction changes, shown an erratic swimming behavior. Energy budgets decreased for lipid (0.01 mg/L DPH) and carbohydrate (10 mg/L DPH) contents. Cholinesterase (neural function) and glutathione S-transferase (Phase II biotransformation/antioxidant processes) increased their activities at 10 mg/L DPH, where a decrease in the total glutathione content (antioxidant system) was observed. DNA damage was found at 0.01 and 10 mg/L DPH. However, a DNA repair occurred after subsequent 72 h in clean media. The in silico study revealed a relevant conservation between human and zebrafish DPH target molecules. These data provide a valuable ecotoxicological information about the DPH effects and MoA to non-target organisms.

Multivariable optimization of activated carbon production from microwave pyrolysis of brewery wastes - Application in the removal of antibiotics from water.

This study aimed at optimizing the one-step chemical activation and microwave pyrolysis of an agro-industrial waste to obtain a microporous activated carbon (AC) with superior textural and adsorptive properties by a fast, low-reagent and low-energy process. Spent brewery grains were used as precursor, and the antibiotics sulfamethoxazole (SMX), trimethoprim (TMP) and ciprofloxacin (CIP) were considered as target adsorbates. A fractional factorial design was applied to evaluate the effect of the main factors affecting the preparation of AC (activating agent, activating agent:precursor ratio, pyrolysis temperature and residence time) on relevant responses. Under optimized conditions (K2CO3 activation, pyrolysis at 800 °C during 20 min and a K2CO3:precursor ratio of 1:2), a microporous AC with specific surface area of 1405 m2 g-1 and large adsorption of target antibiotics (82-94%) was obtained and selected for further studies. Equilibrium times up to 60 min and maximum Langmuir adsorption capacities of 859 µmol g-1 (SMX), 790 µmol g-1 (TMP) and 621 µmol g-1 (CIP) were obtained. The excellent textural and adsorptive properties of the selected material were achieved with a very fast pyrolysis and low load of activating agent, highlighting the importance of optimization studies to decrease the environmental and economic impact of waste-based AC.

Producing Magnetic Nanocomposites from Paper Sludge for the Adsorptive Removal of Pharmaceuticals from Water-A Fractional Factorial Design.

In view of a simple after-use separation, the potentiality of producing magnetic activated carbon (MAC) by intercalation of ferromagnetic metal oxide nanoparticles in the framework of a powder activated carbon (PAC) produced from primary paper sludge was explored in this work. The synthesis conditions to produce cost effective and efficient MACs for the adsorptive removal of pharmaceuticals (amoxicillin, carbamazepine, and diclofenac) from aqueous media were evaluated. For this purpose, a fractional factorial design (FFD) was applied to assess the effect of the most significant variables (Fe3+ to Fe2+ salts ratio, PAC to iron salts ratio, temperature, and pH), on the following responses concerning the resulting MACs: Specific surface area (SBET), saturation magnetization (Ms), and adsorption percentage of amoxicillin, carbamazepine, and diclofenac. The statistical analysis revealed that the PAC to iron salts mass ratio was the main factor affecting the considered responses. A quadratic linear regression model A = f(SBET, Ms) was adjusted to the FFD data, allowing to differentiate four of the eighteen MACs produced. These MACs were distinguished by being easily recovered from aqueous phase using a permanent magnet (Ms of 22-27 emu g-1), and their high SBET (741-795 m2 g-1) were responsible for individual adsorption percentages ranging between 61% and 84% using small MAC doses (35 mg L-1).

In situ functionalization of a cellulosic-based activated carbon with magnetic iron oxides for the removal of carbamazepine from wastewater.

The main goal of this work was to produce an easily recoverable waste-based magnetic activated carbon (MAC) for an efficient removal of the antiepileptic pharmaceutical carbamazepine (CBZ) from wastewater. For this purpose, the synthesis procedure was optimized and a material (MAC4) providing immediate recuperation from solution, remarkable adsorptive performance and relevant properties (specific surface area of 551 m2 g-1 and saturation magnetization of 39.84 emu g-1) was selected for further CBZ kinetic and equilibrium adsorption studies. MAC4 presented fast CBZ adsorption rates and short equilibrium times (< 30-45 min) in both ultrapure water and wastewater. Equilibrium studies showed that MAC4 attained maximum adsorption capacities (qm) of 68 ± 4 mg g-1 in ultrapure water and 60 ± 3 mg g-1 in wastewater, suggesting no significant interference of the aqueous matrix in the adsorption process. Overall, this work provides evidence of potential application of a waste-based MAC in the tertiary treatment of wastewaters. Graphical abstract.

Recent advances on the development and application of magnetic activated carbon and char for the removal of pharmaceutical compounds from waters: A review.

The adsorption of pharmaceutical substances using carbonaceous materials, such as activated carbon (AC), biochar (BC) and hydrochar (HC), has received substantial attention by researchers working on water treatment, due to the simplicity, low-cost and high performance of this process. In order to widen the potentiality of these carbonaceous materials and to overcome some of their limitations, particularly the inefficient separation of powdered formulations from treated water, the incorporation of magnetic nanoparticles has been explored. The recovery of magnetic carbon materials (MCM) from the treated water can be attained by applying an external magnetic field, avoiding inefficient and costly filtration and centrifugation processes, typically applied in the case of non-magnetic carbonaceous adsorbents. In the last ten years, some work has been devoted to the preparation of MCM specifically from AC (MCACM), biochar (MCBCM) and hydrochar (MCHCM). This review aims to present the different aspects of using MCM in water treatment, namely in the removal of pharmaceutical compounds. The synthesis routes used to produce MCM, their physical, morphologic and chemical features, and their application in the removal of these micro-organic contaminants from water will be assessed. The advantages and disadvantages of using MCM in water treatment, and their comparative performance with the carbonaceous non-magnetic precursors will be also discussed in this review.

Investigating the Binding Heterogeneity of Trace Metal Cations With SiO2 Nanoparticles Using Full Wave Analysis of Stripping Chronopotentiometry at Scanned Deposition Potential.

Silica oxides nano- and microparticles, as well as silica-based materials, are very abundant in nature and industrial processes. Trace metal cation binding with these bulk materials is generally not considered significant in speciation studies in environmental systems. Nonetheless, this might change for nanoparticulate systems as observed in a previous study of Pb(II) with a very small SiO2 particle (7.5 nm diameter). Besides, metal binding by those nanoparticles is surprisingly characterized by a heterogeneity that increases with the decrease of metal-to-particle ratio. Therefore, it is interesting to extend this study to investigate different trace metals and the influence of the nanoparticle size on the cation binding heterogeneity. Consequently, the Cd(II), Pb(II), and Zn(II) binding by two different sized SiO2 nanoparticles (Ludox LS30 and TM40) in aqueous dispersion was studied for a range of pH and ionic strength conditions, using the combination of the electroanalytical techniques Scanned Stripping ChronoPotentiometry and Absence of Gradients and Nernstian Equilibrium Stripping. The coupling of these techniques provides the free metal concentration in the bulk (AGNES) and information of the free and complex concentration at the electrode surface for each Stripping Chronopotentiometry at Scanned deposition Potential (SSCP). A recent mathematical treatment allows the reconstruction of a portion of the metal to ligand binding isotherm with the included heterogeneity information using the full SSCP wave analysis. In this work, we observed that the Zn(II) binding is homogeneous, Cd(II) is slightly heterogeneous, and Pb(II) is moderately heterogeneous, whereas the results obtained with the 7.5 nm diameter nanoparticle are slightly more heterogeneous than those obtained with the one of 17 nm. These findings suggest that the Zn(II) binding is electrostatic in nature, and for both Cd(II) and Pb(II), there should be a significant chemical binding contribution.

Multi-element determination of metals and metalloids in waters and wastewaters, at trace concentration level, using electroanalytical stripping methods with environmentally friendly mercury free-electrodes: A review.

Nowadays, water is no longer regarded as an inexhaustible resource and the excessive release and proliferation of toxic metal(loid)s into aquatic environments has become a critical issue. Therefore, fast, accurate, simple, selective, sensitive and portable methodologies to detect multiple elements in natural waters is of paramount importance. Electrochemical stripping analysis is an efficient tool for trace metal(loid)s determinations and bring new prospects for answering the current environmental concerns. This review presents a survey of the advancements made between 2003 and 2016 on the development and application of non-toxic mercury free electrodes on the simultaneous analysis of metals and metalloids in waters and wastewaters by means of electroanalytical stripping techniques. The advantages, limitations, improvements and real applications of these "green" sensors are discussed from a critical point of view.

A macroalgae-based biotechnology for water remediation: Simultaneous removal of Cd, Pb and Hg by living Ulva lactuca.

Metal uptake from contaminated waters by living Ulva lactuca was studied during 6 days, under different relevant contamination scenarios. In mono-metallic solutions, with concentrations ranging from 10 to 100 µg L-1 for Hg, 10-200 µg L-1 for Cd, and 50-1000 µg L-1 for Pb, macroalgae (500 mg L-1, d.w.) were able to remove, in most cases 93-99% of metal, allowing to achieve water quality criteria regarding both surface and drinking waters. In multi-metallic solutions, comprising simultaneously the three metals, living macroalgae still performed well, with Hg removal (c.a. 99%) not being significantly affected by the presence of Cd and Pb, even when those metals were in higher concentrations. Removal efficiencies for Cd and Pb varied between 57 and 96%, and 34-97%, respectively, revealing an affinity of U. lactuca toward metals: Hg > Cd > Pb. Chemical quantification in macroalgae, after bioaccumulation assays demonstrated that all Cd and Hg removed from solution was really bound in macroalgae biomass, while only half of Pb showed to be sorbed on the biomass. Overall, U. lactuca accumulated up to 209 µg g-1 of Hg, up to 347 µg g-1 of Cd and up to 1641 µg g-1 of Pb, which correspond to bioconcentration factors ranging from 500 to 2200, in a dose-dependent accumulation. Pseudo-first order, pseudo-second order and Elovich models showed a good performance in describing the kinetics of bioaccumulation, in the whole period of time. In the range of experimental conditions used, no mortality was observed and U. lactuca relative growth rate was not significantly affected by the presence of metals. Results represent an important contribution for developing a macroalgae-based biotechnology, applied for contaminated saline water remediation, more "green" and cost-effective than conventional treatment methods.

Bioaccumulation of Hg, Cd and Pb by Fucus vesiculosus in single and multi-metal contamination scenarios and its effect on growth rate.

Results of 7-days exposure to metals, using environmentally realistic conditions, evidenced the high potential of living Fucus vesiculosus to remove Pb, Hg and Cd from contaminated salt waters. For different contamination scenarios (single- and multi-contamination), ca 450 mg L-1 (dry weight), enable to reduce the concentrations of Pb in 65%, of Hg in 95% and of Cd between 25 and 76%. Overall, bioconcentration factors ranged from 600 to 2300. Elovich kinetic model described very well the bioaccumulation of Pb and Cd over time, while pseudo-second-order model adjusted better to experimental data regarding Hg. F. vesiculosus showed different affinity toward studied metals, following the sequence order: Hg > Pb > Cd. Analysis of metal content in the macroalgae after bioaccumulation, proved that all metal removed from solution was bound to the biomass. Depuration experiments reveled no significant loss of metal back to solution. Exposure to contaminants only adversely affected the organism's growth for the highest concentrations of Cd and Pb. Findings are an important contribute for the development of remediation biotechnologies for confined saline waters contaminated with trace metal contaminants, more efficient and with lower costs than the traditional treatment methods.

Determination of the Free Metal Ion Concentration Using AGNES Implemented with Environmentally Friendly Bismuth Film Electrodes.

Ex situ plated Bi film electrodes (Bi-FE) have been employed, for the first time, to measure the free concentration of Pb(II) in aqueous solutions using absence of gradients and Nernstian equilibrium stripping (AGNES) with stripping chronopotentiometry (SCP) quantification. The amount of deposited Pb°, below a certain threshold, follows a Nernstian relationship with the applied potential. This threshold can be interpreted as the frontier of transition from surface deposition to solid (bulk) formation of Pb°. AGNES with Bi-FE yielded a very good detection limit (3σ) for Pb(II) of 6.0 × 10(-9) M with an applied gain of 398 and a deposition time of 400 s. The ability of the Bi film electrode to perform speciation measurements was demonstrated for Pb(II)-PSS and Pb(II)-IDA systems. The measured values with the Bi-FE were in good agreement with the values obtained using the Hg film electrode and/or the values reported in the literature.

A multidisciplinary approach to evaluate the efficiency of a clean-up technology to remove mercury from water.

A microporous material denoted ETS-4 was used as the decontaminant agent to treat water with a low level of Hg contamination. The effectiveness of the treatment was evaluated by assessment of the efficiency of Hg removal and ecotoxicological responses. The results showed that under highly competitive conditions the removal of Hg ranged between 58 % and 73 % depending upon the initial Hg concentration, and that Hg removal was reflected in decreased toxicity to some organisms. The ecotoxicological data indicated that the bacterium Vibrio fischeri was the least sensitive organism tested, as no toxicity was observed in either pre- or post-treatment waters. Daphnia magna was highly sensitive to Hg. Mercury removal by ETS-4 was not sufficient to completely remove the toxicity of Hg to D. magna. However, it was effective in the complete reduction of toxicity for the green alga, Pseudokirchneriella subcapitata.

Efficiency of a cleanup technology to remove mercury from natural waters by means of rice husk biowaste: ecotoxicological and chemical approach.

In the present work, the efficiency of rice husk to remove Hg(II) from river waters spiked with realistic environmental concentrations of this metal (µg L(-1) range) was evaluated. The residual levels of Hg(II) obtained after the remediation process were compared with the guideline values for effluents discharges and water for human consumption, and the ecotoxicological effects using organisms of different trophic levels were assessed. The rice husk sorbent proved to be useful in decreasing Hg(II) contamination in river waters, by reducing the levels of Hg(II) to values of ca. 8.0 and 34 µg L(-1), for an Hg(II) initial concentration of 50 and 500 µg L(-1), respectively. The remediation process with rice husk biowaste was extremely efficient in river waters spiked with lower levels of Hg(II), being able to eliminate the toxicity to the exposed organisms algae Pseudokirchneriella subcapitata and rotifer Brachionus calyciflorus and ensure the total survival of Daphnia magna species. For concentrations of Hg(II) tenfold higher (500 µg L(-1)), the remediation process was not adequate in the detoxification process, still, the rice husk material was able to reduce considerably the toxicity to the bacteria Vibrio fischeri, algae P. subcapitata and rotifer B. calyciflorus, whose responses where fully inhibited during its exposure to the non-remediated river water. The use of a battery of bioassays with organisms from different trophic levels and whose sensitivity revealed to be different and dependent on the levels of Hg(II) contamination proved to be much more accurate in predicting the ecotoxicological hazard assessment of the detoxification process by means of rice husk biowaste.

Competitive effects on mercury removal by an agricultural waste: application to synthetic and natural spiked waters.

In this work, the efficiency of a local and highly, available agricultural waste, the raw rice husk, was used to remove mercury (Hg) from synthetic and natural waters, spiked with concentrations that reflect the contamination problems found in the environment. Different operating conditions were tested, including initial pH, ionic strength, the presence of co-ions (cadmium) and organic matter. The sorption efficiency of rice husk was slightly affected by the presence H+ ions (pH range between 3 and 9), but in the presence of NaNO3 and NaCl electrolytes and in binary solutions containing Cd2+ and H2+, the sorption efficiency was dependent on the nature and levels of the interfering ion and on the initial concentration of Hg+ used. Nevertheless, in a situation of equilibrium the effect of those ions was negligible and the removal efficiency ranged between 82% and 94% and between 90% and 96% for an initial Hg2+ concentration of 0.05 mg L(-1) and 0.50 mg L(-1), respectively. In more complex matrices, i.e. in the presence ofhumic substances and in natural river waters, the speciation and dynamics of Hg was changed and a fraction of the metal becomes unavailable in solution. Even then, the values obtained for Hg removal were satisfactory, i.e. between 59% and 76% and 81% and 85% for an initial concentration of Hg2+ of 0.05 and 0.50 mg L(-1), respectively.

Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions.

The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 µg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 µg/L.

Evaluation of thin mercury film rotating disk electrode to perform absence of gradients and Nernstian equilibrium stripping (AGNES) measurements.

In the present work, the applicability of thin mercury film on a rotating disk electrode (TMF-RDE), to assess the free metal ion concentration by the absence of gradients and Nernstian equilibrium stripping (AGNES), is evaluated. The thickness of the mercury film and several AGNES parameters has been optimized. A nominal 16 nm film is chosen due to the higher signal (faradaic current) relative to the value of the noise (capacitive current). Due to the smaller volume to area ratio, the deposition time needed to reach a certain preconcentration factor (Y) is much shorter than in larger electrodes, like the HMDE. The limit of detection (3 sigma) for lead(II) is 7.4 x 10(-9)M and 7.2 x 10(-8)M for a Y of 5000 (deposition time of 150 s) and 1000 (deposition time of 100 s), respectively. A specific mathematical treatment is developed in order to subtract a corrected blank taking into account the degradation of the thin film (presumably, falling down of drops). The couple TMF-RDE/AGNES is successfully applied for speciation purposes in the systems Pb(II)-latex nanospheres and Pb(II)-IDA (iminodiacetic acid), where the stability constants calculated for both systems agree with values reported in the literature.

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.

Ion-exchange voltammetry of dopamine at Nafion-coated glassy carbon electrodes: quantitative features of ion-exchange partition and reassessment on the oxidation mechanism of dopamine in the presence of excess ascorbic acid.

The incorporation/exclusion features of dopamine (DA), ascorbic acid (AA) and uric acid (UA) are evaluated for Nafion (NA)-coated glassy carbon electrodes (GCE) of different thicknesses. The ion-exchange partition of DA(+) between the NA film and the sodium phosphate electrolyte is evaluated by determining the partition coefficient (k(D)) and the apparent diffusion coefficient (D(app)) in thick NA films which were 401 and 1.5 x 10(-9) cm(2) s(-1), respectively. The solution diffusion coefficient was found to be 6.0 x 10(-6) cm(2) s(-1). Also, the effect of NA loading and of the voltammetric timescale on DA voltammetry in the presence of excess AA is assessed, at physiologic like conditions. It is demonstrated that, although AA is excluded at the NA coating, a catalytic regeneration of DA, induced by AA, occurs at the interface NA film/electrolyte resulting from the diffusion of the o-quinone product of DA oxidation from the electrode surface to that interface. The interference of AA in the voltammetric signal of DA is eliminated using 18 microg mm(-2) NA films and v> or =0.5 V s(-1). Therefore, fast, selective and sensitive voltammetric analysis of DA at concentrations<100 microM in the presence of excess AA, e.g., 1 mM is achieved.