Effect of the deposition potential on the voltammetric determination of complexing ligand concentrations in sea-water.

The effect of the deposition potential on the determination of complexing ligand concentrations in natural waters was investigated by titration with Cu from sea-water samples originating from the North Sea and monitoring the labile Cu concentration after deposition at two potentials, viz., -0.05 and -0.7 V. The amount of deposited metal was measured by cathodic stripping voltammetry with ligand competition, using tropolone as the added ligand. It was found that the complexing ligand concentration detected decreased by more than 60% when the more negative deposition potential was applied. The data indicate that a significant fraction of the organic complexes of Cu in natural waters is electrochemically labile at negative deposition potentials and is not determined by anodic stripping voltammetry. The concentrations and conditional stability constants of the complexing ligands in the North Sea are similar to those detected previously in the Irish Sea.     

Research on Electroanalytical Chemical Methods for Trace Metal Speciation in Sea Water Samples

Since bioavalability of a trace metal in natural waters is affected by its chemical forms, the speciation of a trace metal becomes more and more important in environmental chemistry. Differential pulse anodic stripping voltammetry (DPASV) titration procedures are developed and applied to identify organic trace metal species of copper (Cu), lead (Pb) and zinc (Zn) in sea water and to determine their complexing capacity.     

Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters

Progress in marine chemistry has been driven by improved sampling and sample handling techniques, and developments in analytical chemistry. Consequently, during the last 20 years our understanding of marine trace metal biogeochemistry has improved a great deal. Stripping voltammetric techniques (anodic stripping voltammetry and adsorptive cathodic stripping voltammetry) have made an important contribution to this understanding. The selectivity and extremely low detection limits have made stripping voltammetry a widely used technique for trace metal speciation and trace metal distribution measurements in seawater. Stripping voltammetry is very suitable for ship-board and in-situ applications because of the portability, low cost and capability for automation of the voltammetric instrumentation. Future developments in stripping voltammetry can be expected in the field of stand-alone submersible voltammetric analysers, capable of continuous trace metal measurements. Future applications of stripping voltammetry can be found in the interactions between trace metal speciation and growth and the functioning of organisms in pristine and metal polluted marine waters.     

Stripping voltammetric detection in high-precision titrimetry

Anodic stripping voltammetry is used to detect the equivalence point in compleximetric titration. The sensitivity of detection thus provided enables the attainable precision to be markedly improved. Theoretical treatment of the electrochemical deposition of a metal from media containing a complexing agent such as EDTA in large excess is based on the model of reversible reduction of the complex formed, as worst case. It is shown that anodic stripping voltammetry can be applied if the conditional stability constant of the complex is appropriate. Semi-automatic techniques are outlined for improving the speed and ease of operation. Indium, cadmium, and bismuth can be titrated with EDTA, with a relative standard deviation of less than 0.01%.     

Computerized electroanalysis: Part II1. Multiple scanning and background subtraction,a new technique for stripping analysis

A method of registering the pure Faradaic current in anodic stripping voltammetry is described. A computer-controlled voltammetric unit is used. The chemical significance or the voltammograms obtained is discussed. Details of the computer algorithm and results from anodic stripping analysis of metal solutions are given. The design of a mercury-plated glassy carbon electrode is discussed.     

Determination of mobile form contents of Zn, Cd, Pb and Cu in soil extracts by combined stripping voltammetry

The amount of mobile forms of Zn, Pb, Cd and Cu in extracts obtained by treating soil samples with ammonium nitrate were determined by an appropriate combination of anodic and cathodic stripping voltammetry with hanging mercury drop electrode. Every analysis required three mercury drops: on the first one, zinc was determined; on the second, cadmium and lead; on the third, copper was determined. Zinc, lead and cadmium were determined by conventional differential-pulse anodic stripping voltammetry. For copper determination, adsorptive differential-pulse cathodic stripping voltammetry with amalgamation using chloride ions as a complexing agent was applied. The standard deviation of the results was from 1 to 10% depending on the metal content in the sample. Voltammetric results were in good agreement with the AAS analysis. No microwave digestion of soil extracts was necessary.     

Cadmium Complexation in Culture Media

Square‐wave anodic stripping voltammetry (SW‐ASV) has been applied to monitor changes in the complexing capacity (CC) in a microbiological culture medium through different physiological states, focusing on cadmium interactions with the potential ligands. Total ligand concentration (Lt) is evaluated both from the titration curve and Ruzic linearization, with good agreement between the methods. Values obtained for the conditional stability constant suggest the occurrence of moderate ligands. Results show that the studied culture medium is capable of complexing cadmium and that the complexing capacity is affected by the physiological states of bacteria.     

Voltammetric methods for speciation analysis of trace metals in natural waters

Trace metals play an important role in the regulation of primary productivity and phytoplankton community composition. Metal species directly affects the biogeochemical cycling processes, transport, fate, bioavailability and toxicity of trace metals. Therefore, developing powerful methods for metal speciation analysis is very useful for research in a range of fields, including chemical and environmental analysis. Voltammetric methods, such as anodic stripping voltammetry (ASV) and competing ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV), have been widely adopted for speciation analysis of metals in different natural aquatic systems. This paper provides an overview of the theory of voltammetric methods and their application for metal speciation analysis in natural waters, with a particular focus on current voltammetric methods for the discrimination of labile/inert fractions, redox species and covalently bound species. Speciation analysis of typical trace metals in natural waters including Fe, Cu, Zn, Cd, and Pb are presented and discussed in detail, with future perspectives for metal speciation analysis using voltammetric methods also discussed. This review can elaborate the particular knowledge of theory, merits, application and future challenge of voltammetric methods for speciation analysis of trace metals in natural waters.     

Detection of aniline at boron-doped diamond electrodes with cathodic stripping voltammetry

Boron-doped diamond (BDD) electrodes were used to investigate the possibility of detecting aniline by linear-sweep cathodic stripping voltammetry. It was found that the dimeric species (p-aminodiphenylamine and benzidine) formed by anodic oxidation of aniline during the accumulation period are involved in electrochemically reversible redox processes and, in acidic media, the shape of the stripping voltammetric response is suitable for aniline detection in the micromolar concentration range. The low background current of conductive diamond is an advantage compared to other electrode materials and allows a detection limit of 1 μM. Weak adsorption properties and the extreme electrochemical stability are additional advantages of BDD and it was found that, even after long-time measurements, the electrode surface can regain its initial activity by an anodic polarization in the potential region of water decomposition.     

Determination of Thiols and Disulfides in Whole Blood and Its Fractions by Anodic Stripping Voltammetry and Anodic Stripping Voltammetric Titration

SH‐ and SS‐groups content and their ratio is one of the most important factors of organism antioxidant system. Change in ratio of thiols to disulfides can serve as an indicator of oxidative stress. Anodic stripping voltammetry and anodic stripping voltammetric titration (direct and reverse variants) methods are proposed for determination of thiols and disulfides concentration. Disulfides are preliminary reduced with sodium sulfite. Ag⁺+RSH→AgSR+H⁺ reaction is used to provide the information. Unreacted silver ions concentration is determined by anodic stripping voltammetry method using platinum working electrode. Calibration free method is suggested. The possibilities of express analysis of blood and its fractions are described. Reliability of results and accuracy are confirmed by model solutions analysis and recovery study of whole blood and its fractions. Results of whole blood, erythrocyte mass, plasma and serum taken from different groups of patients' investigations are given, that demonstrate perspectives of the application methods in clinical practice.     

Voltammetric method for the determination of Zn,Cd, Pb,Cu and Ni in interstitial water

To determine heavy metals in interstitial water from Baltic sea sediments a sampling method with subsequent voltammetric determination is described. Copper, lead, zinc and cadmium are determined in the UV-digested samples of interstitial water by differential pulse anodic stripping voltammetry while nickel is determined by adsorption voltammetry. The determination of five metals in one sample in a wide concentrations range is possible using a low cost apparatus. The profiles of the metal concentrations in interstitial water of subsequent layers of sediments, sampled from Puck Bay, Gdańsk Bay, the Bornholm area and the S?upsk area are presented.     

The differential pulse anodic stripping voltammetry of copper and lead and their determination in EDTA extracts of soils with the mercury film glassy carbon electrode

The differential pulse anodic stripping voltammetry of copper and lead at the mercury film glassy carbon electrode is discussed. The mercury film prevents the occurrence of a monolayer stripping peak for copper. The influence of antimony and bismuth on the anodic stripping voltammetric behaviour of copper and lead is discussed. An interaction between copper and antimony distorts the copper stripping peak and gives rise to an intermediate peak. The method described is suitable for determining copper and lead simultaneously in EDTA extracts of soils.     

Simultaneous determination of trace amounts of zinc, lead and copper in rum by anodic stripping voltammetry

The determination of traces of Zn, Pb and Cu in rum samples by anodic stripping voltammetry without previous treatment or addition of a supporting electrolyte, using a hanging mercury drop electrode, is described. The choice of an appropriate stripping voltammetric method and deposition potential minimizes the influence of the organic content and ensures good reproductibility of the measurements. The reliability of the method was tested by comparing the results with those given by absorption spectrometry, the differences being about 10%. The method allows heavy metal ions to be determined in the mug l(-1) concentration range.     

Voltammetric study of some macromolecule - metal complexes

The usefulness of a voltammetric model for studying macromolecule - metal complex systems is verified. Complexes formed by a metal ion (Zn(II), Cd(II), Pb(II) or Cu(II)) and a macromolecule (polymethacrylic (PMA), polyacrylic (PAA), alginic (AA) or polygalacturonic (PGA) acids) are investigated. Several voltammetric techniques have been used: sampled direct current polarography (DCP), normal pulse polarography (NPP), differential pulse polarography (DPP), reverse pulse polarography (RPP), cyclic voltammetry (CV) and differential pulse anodic stripping voltammetry (DPASV). Results confirm the validity of the model, in determining not only formation constants but also diffusion coefficients of the complexes. The behaviour of some systems agrees with that predicted by the model. Nonetheless, other systems only partially fulfil the predictions for different reasons, which are discussed.     

Application of an autoranging amplifier in the simultaneous determination of trace heavy metals by anodic stripping voltammetry

An autoranging amplifier with a gain of 1–1000 is described, together with its possible application in anodic stripping voltammetry. The performance of the amplifier is demonstrated by differential-pulse anodic stripping voltammetric analysis of stored sea-water, in the subtractive mode with two working electrodes. It is suggested that the autoranging amplifier could save considerable analysis time by eliminating the need for trial runs for gain adjustments and by relieving the operator from the need to change the recorder scale during the analysis.     

Application of multivariate curve resolution to the voltammetric study of the complexation of fulvic acids with cadmium(II) ion

The interaction of fulvic acids with Cd(II) ions has been studied by differential pulse anodic stripping voltammetry (ASV), at pH 7.0 and 0.1 M KNO₃. Voltammetric data obtained during the titration of mixtures of Cd(II) and fulvic acids at different concentrations have been analyzed using multivariate curve resolution (MCR). The application of this method allowed the resolution of the major contributions involved in the titration experiments. Apart from free Cd(II), two more contributions related with the complexation process were detected and resolved, and their corresponding pure voltammograms and concentration profiles were estimated. Simultaneous analysis of independent voltammetric titrations using the proposed MCR methods is shown extremely recommended because it overcame some of the limitations observed in the analysis of individual titrations.     

Multivariate curve resolution of overlapping voltammetric peaks: quantitative analysis of binary and quaternary metal mixtures

The application of multivariate curve resolution-alternating least squares (MCR-ALS) to the quantitative analysis of different metal ion mixtures using voltammetric data is described. The performance of MCR-ALS was evaluated in the resolution and quantitation of overlapped voltammetric peaks obtained in the analysis of binary and quaternary mixtures of Cd(II), In(III), Pb(II) and Tl(I) metal ions by anodic stripping voltammetry. Quality assessment of qualitative and quantitative determinations was evaluated considering the effects of different constraints and of initial estimations. MCR-ALS results were validated and compared with those obtained by applying other well-established multivariate calibration methods, such as partial least squares (PLS) and direct classical least squares (DCLS) methods.     

Bismuth film electrode for anodic stripping voltammetric determination of tin

The bismuth film electrode (BiFE), in combination with anodic stripping voltammetry, offers convenient measurement of low concentrations of tin. The procedure involves simultaneous in situ formation of the bismuth film electrode on a glassy carbon substrate electrode, together with electrochemical deposition of tin, in a non-deaerated model solution containing bismuth ions, catechol as complexing agent and the metal analyte, followed by an anodic stripping scan. The BiFE is characterized by an attractive electroanalytical performance, with two distinct voltammetric stripping signals corresponding to tin, accompanied with low background contributions. Several experimental parameters were optimized, such as concentration of bismuth ions and catechol, deposition potential, deposition time and pH of the model solution. In addition, a critical comparison is given with bare glassy carbon and mercury film electrodes, revealing the superior characteristics of BiFE for measurement of tin. BiFE exhibited highly linear behavior in the examined concentration range from 1 to 100 μg L⁻¹ of tin (R² = 0.997), an LoD of 0.26 μg L⁻¹ tin, and good reproducibility with a calculated R.S.D. of 7.3% for 10 μg L⁻¹ tin (n = 10). As an example, the practical applicability of BiFE was tested with the measurement of tin in a real sample of seawater.     

Analytical methods for determination of free metal ion concentration, labile species fraction and metal complexation capacity of environmental waters: A review

Different experimental approaches have been suggested in the last few decades to determine metal species in complex matrices of unknown composition as environmental waters. The methods are mainly focused on the determination of single species or groups of species.The more recent developments in trace elements speciation are reviewed focusing on methods for labile and free metal determination.Electrochemical procedures with low detection limit as anodic stripping voltammetry (ASV) and the competing ligand exchange with adsorption cathodic stripping voltammetry (CLE-AdCSV) have been widely employed in metal distribution studies in natural waters. Other electrochemical methods such as stripping chronopotentiometry and AGNES seem to be promising to evaluate the free metal concentration at the low levels of environmental samples. Separation techniques based on ion exchange (IE) and complexing resins (CR), and micro separation methods as the Donnan membrane technique (DMT), diffusive gradients in thin-film gels (DGT) and the permeation liquid membrane (PLM), are among the non-electrochemical methods largely used in this field and reviewed in the text. Under appropriate conditions such techniques make possible the evaluation of free metal ion concentration.     

Effects of the detection window on the determination of organic copper speciation in estuarine waters

The complexation of copper by natural organic ligands in sea water was measured by cathodic stripping voltammetry with ligand (catechol and quinolin-8-ol) competition. Two methods to determine copper complexation in estuarine waters were compared, one based on a complete titration of the complexing capacity of the sample and the other on measurement of the labile and total dissolved metal concentrations only. Values for log α_CuL (ihe α-coefficient for complexation of Cu²⁺ by natural organic ligands) ranging from 3.2 to 7.7 and from 3.3 to 7.8 could be detected by varying long α_CuAL (the α-coefficient for complexation of Cu²⁺ by the added competing ligand) from 3.4 to 8.9 in samples from the Tamar estuary and from the Channel. The two methods gave comparable results and showed that the type of sites detected depends on the detection window of the technique. This effect is due to the sea and estuarine water samples containing a series of complexing ligands forming complexes of greatly varying strength, thus causing a rnage of complex stabilities to be measured as a function of the detection window of each technique. A comparison showed that lower values for α_CuL are obtained by anodic stripping voltammetry as a result of that technique having a lower detection window. A detailed study of the Tamar estuary revealed a decrease in log α_CuL from 10.8 to 8.3 with increasing salinity, demonstrating that major cations compete with copper for the complexing sites. The free Cu²⁺ concentrations were very low throughout the estuary (16.2 < pCu²⁺ < 18.2) even though the total measurements to establish potential toxic effects of copper in natural waters.