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.     

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.     

铟(Ⅲ)-向红菲啰啉络合物的吸附伏安法研究

运用1 5次微分伏安法 ,常规溶出伏安法及循环伏安法研究了铟(Ⅲ) -向红菲啉络合物在汞电极上的电化学行为 ,讨论了络合物的形成机理及条件 ,建立了测试痕量铟的新方法 ,运用该法对样品中痕量铟进行了测试 ,结果令人满意。     

Electrochemical methods for monitoring of environmental carcinogens

The use of modern electroanalytical techniques, namely differential pulse polarography, differential pulse voltammetry on hanging mercury drop electrode or carbon paste electrode, adsorptive stripping voltammetry and high performance liquid chromatography with electrochemical detection for the determination of trace amounts of carcinogenic N-nitroso compounds, azo compounds, heterocyclic compounds, nitrated polycyclic aromatic hydrocarbons and aromatic and heterocyclic amines is discussed. Scope and limitations of these methods are described and some practical applications based on their combination with liquid-liquid or solid phase extraction are given.     

Renewable Pencil Electrodes for Highly Sensitive Anodic Stripping Voltammetric Determination of 3‐Hydroxyflavone and Morin in Bulk Form and in Biological Fluids

An electrochemical anodic adsorptive stripping procedure for ultra‐trace assay of 3‐hydroxyflavone (3HF) and Morin at a renewable pencil electrode (PGE) in bulk form and in biological fluids is described. The nature of the oxidation process of 3HF and Morin taking place at the PGE was characterized by cyclic voltammetry. The results show that the determination of the oxidation peak current is the basis of a simple, accurate and rapid method for quantification of 3HF by square‐wave anodic stripping voltammetry. Determination of Morin was achieved by square‐wave anodic adsorptive stripping voltammetry of the formed Morin? Cu(II) complex at a PGE. Factors influencing the trace measurements of 3HF and the Morin? Cu (II) complex at a PGE are assessed. The limits of detection and quantitation for the determination of 3HF and Morin in bulk form and in biological fluids were determined. The statistical analysis and the calibration curve data for trace determination of 3HF and Morin are reported.     

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.     

Novel disposable bismuth-sputtered electrodes for the determination of trace metals by stripping voltammetry

This work describes a novel type of bismuth electrode for stripping voltammetry based on coating a silicon substrate with a thin bismuth film by means of sputtering. The bismuth-based sensors were characterized by optical methods (scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD)) and as well as by linear sweep voltammetry. Subsequently, the electrodes were tested for the detection of low concentrations of trace metals (Cd(II), Pb(II) and Ni(II)) by stripping voltammetry. Well-formed stripping peaks were observed for trace concentrations of the target analytes demonstrating “proof-of-principle” for these sensors. This type of electrochemical device, utilizing thin-film technology for the formation of the bismuth film, holds promise for future applications in trace metal analysis.     

Recent Advances in Voltammetry

Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler–Volmer and Marcus–Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of ‘nano-impacts’.     

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%.     

Sonoelectrochemical investigation of silver analysis at a highly boron-doped diamond electrode

A study into the sonoelectroanalysis of silver at a highly boron-doped diamond electrode is presented, exploring the benefits of the introduction of power ultrasound and new electrode materials into classical electrochemical techniques. Both cathodic and anodic stripping voltammetry have been investigated in terms of their analytical suitability towards silver detection. Cathodic stripping voltammetry, via electrodeposited silver oxide, was affected by the unusual chemistry of the highly oxidising Ag(2+) species and the characterisation of this system is discussed in detail. Anodic stripping, via deposition of metallic silver on the bare boron-doped diamond electrode surface under ultrasound, coupled with square-wave voltammetry, was successfully employed in the development of a sensitive technique for the analysis of trace silver ions. A detection limit for Ag(+) of 10(-9) M for a 300-s deposition, with a linear range of at least two orders of magnitude, and the beneficial effects of controlling the speciation of Ag(+) via complexation with chloride ions are reported.     

Chelate adsorption for trace voltammetric measurements of 2-thiouracil and 4-thiouridine

A very sensitive electrochemical stripping method for trace measurements of 2-thiouracil and 4-thiouridine in presence of Cu(II) is described. The chelate of Cu(II) with 2-thiouracil and 4-thiouridine is adsorbed on the hanging mercury drop electrode, and the reduction current of the accumulated complex is measured by cathodic stripping voltammetry. The adsorption and redox behaviour are indicated by cyclic voltammetry. Optimum experimental conditions include a preconcentration potential of 0.0 V, solution of pH 7.2, adsorption time 5 min, pulse amplitude 100 mV, and a linear scan mode. The sharp chelate peak, associated with the effective interfacial accumulation, coupled with the flat baseline, facilitates measurements at the nanomolar and submicromolar concentration levels.     

An Electrochemical Robotic System for Routine Cathodic Adsorptive Stripping Analysis of Ni2+ Ion Release from Corroding NiTi Shape Memory Alloys

Cathodic adsorptive stripping voltammetry (AdSV) as highly sensitive and selective method for quantifying trace amounts of dissolved Ni²⁺‐ions has been integrated into an electrochemical robotic device using the wells of microtiter plates as low‐volume electrochemical cells. A three‐electrode assembly integrating a Bismuth film‐modified glassy carbon electrode as working electrode and a glass capillary for delivering Ni²⁺ standard solution in conjunction with an adapted software allowed multiple AdSV measuring cycles to be performed one after the other in the individual compartments of a 24‐well microtiter plate. Of advantage for the automation was the possibility of an in‐well electrochemical removal of used and a replating of fresh Bi films in between distinct measuring cycles. With optimized parameters for the accumulation of the complex between Ni²⁺‐ions and dimethylglyoxime onto the surface of the Bi film electrode and the subsequent stripping procedure, automated adsorptive stripping voltammetry in the established system offered a linear dynamic range of up to 170 nM, a sensitivity of 12 nA/nM Ni²⁺ and a limit of of detection of 2.1 nM (N=16) for the detection of trace levels of Ni²⁺‐ions. Automated AdSV certainly is of convenience for studying larger number of samples due to the high‐throughput capability of the robotic apparatus. As example, the automatic quantification of Ni²⁺‐ion release from electropolished surfaces of NiTi shape memory alloys during corrosion in NaCl solutions is described.     

Abrasive stripping voltammetry — an electrochemical solid state spectroscopy of wide applicability

Abrasive stripping voltammetry is a new electroanalytical technique designed for the qualitative and quantitative analysis of solid materials. It is based upon a preliminary mechanical transfer of trace amounts of a solid sample onto the surface of an electrode. All conventional electrochemical measuring methods can be used. The technique is applicable in many fields of solid state analysis and for fundamental studies of the electrochemistry of solid compounds.     

Anodic stripping voltammetry with carbon paste electrodes for rapid Ag(I) and Cu(II) determinations

The simultaneous determination of silver(I) and copper(II) is realized for the routine analysis of trace levels of these elements by anodic stripping voltammetry (ASV) at the carbon paste electrode (CPE). The electrochemical response is studied in 14 different supporting electrolytes, ranging from acidic solutions (pH 0.1) to neutral and basic (pH 9.7) media, and the parameters governing electrodeposition and stripping steps are characterized for each medium by the use of pseudo-voltammograms. Comparison between different modes of matter transport mechanisms is also given. The dynamic range of the method is 0.05 to 150 mug 1(-1) Ag(I) in the majority of the media studied and can be extended to 400 mug l(-1) in selected media, with a general reproducibility in the +/- 2% range for five replicate measurements. The total analysis time lies between approximately 30 s and 10 min. Activation of the CPE surface has been studied, but this pretreatment is demonstrated to be unfavourable and is replaced by a simpler unique 'cleaning' procedure of dipping the CPE in diluted nitric acid.     

Electrochemical monitoring of biogenic microelements

This paper reviews literary data on electrochemical monitoring of biogenic microelements in natural and industrial objects. Special attention is paid to the questions of the trace determination for a number of transition metals by stripping voltammetry (SVA) after the adsorptive enrichment of these elements as dimethylglyoxime (DMG) complexes on the surface of a working electrode. The analytical possibilities of adsorptive SVA with the use of mercury-based and mercury-free electrodes are compared. The paper is dedicated to the memory of Vadim Mikhailovich Ivanov.     

Stripping voltammetry method for determination of manganese as complex with oxine at the carbon paste electrode with and without modification with montmorillonite clay

Oxine (8-hydroxyquinoline) was used as an efficient and selective ligand for stripping voltammetry trace determination of Mn(II). A validated square-wave adsorptive cathodic stripping voltammetry method has been developed for determination of Mn(II) selectively as oxine complex using both the bare carbon paste electrode (CPE) and the modified CPE with 7 % (w/w) montmorillonite-Na clay. Modification of carbon paste with montmorillonite clay was found to greatly enhance its adsorption capacity. Limits of detection of 45 ng l^?1 (8.19?×?10^?10 mol L^?1) and 1.8 ng l^?1 (3.28?×?10^?11 mol L^?1) Mn(II) were achieved using the bare and modified CP electrodes, respectively. The achieved limits of detection of Mn(II) as oxine complex using the modified CPE are much sensitive than the detection limits obtained by most of the reported electrochemical methods. The developed stripping voltammetry method using both electrodes was successfully applied for trace determination of Mn(II) in various water samples without interferences from various organic and inorganic species.     

Electrochemical Behavior of Crystal Violet on Glassy Carbon Electrodes

The electrochemical behavior of Crystal Violet (CV) on the surface of a glassy carbon electrode in potassium chloride, nitrate, and iodide supporting electrolytes was studied using stripping voltammetry. It was demonstrated that an electroactive complex of CV with iodine was adsorbed on the electrode in a KI solution. This property can be used for determining iodide by adsorption–stripping voltammetry.     

Trace analysis by polarography and voltammetry in pharmaceutical and environmental chemistry

Differential pulse polarography (d.p.p.), anodic and cathodic stripping voltammetry (a.s.v. and c.s.v.) and on-line electrochemical detection (e.g., HPLC-e.d.) have been extensively exploited in recent years for the determination of trace concentrations of many organic and organometallic molecules of biological significance. Such analyses can be carried out in complex matrices such as body fluids, foods, agricultural materials and aquatic matrices^1,2,3.     

Recent advances in stripping analysis

Summary A review is given of the key developments of stripping voltammetry in recent years. Important advances such as non-electrolytic (adsorptive) preconcentration schemes, modified or ultramicro stripping electrodes, and versatile and rapid flow systems are discussed. Such developments substantially enhance the analytical power of stripping voltammetry, allowing it to retain its place as one of the most useful techniques for trace analysis.     

Chemically modified electrode for the determination of gold — an electrochemical and spectrophotometric study

The voltammetric determination of trace amounts of gold has been studied using a chemically modified electrode. The role played by the host molecule attached to a glassy carbon electrode (GCE), i.e. 8,9,17,18-dibenzo-1,7-dioxa-10,13,16-triazacyclooctadecane (DDTC), was examined by electrochemical and spectrochemical techniques. Cathodic stripping voltammetry (CSV) was applied to study the various parameters affecting the affinity of gold ions by a DDTC modified electrode as well as the interference by other ions. Finally, the method has been successfully applied to determine gold traces in a geological sample. In addition, the formation of an AuCl ₄ ^– -DDTC complex was followed and its formation constant was determined by spectrophotometry.