On-site determination of Pb2+ and Cd2+ in seawater by double stripping voltammetry with bismuth-modified working electrodes

To meet the urgent requirement of determining trace Pb2+ and Cd2+ in seawater on site, herein we developed a simple but novel electrochemical method, named as double stripping voltammetry, using only a portable heavy metal analyzer. The proposed method consisted of three steps: First, the targeted heavy metal ions in bulk solution were concentrated onto an ionic liquid-graphite-based paste working electrode (ILGPE), which exhibits a dramatic ability of accumulation, by electrodeposition in the presence of Bi3+. Second, the three-electrode arrangement, including the ILGPE loaded with the reduced products, was transferred into 1.0mL acetate buffer solution, followed by a stripping procedure. Third, the measurement was performed with the other stripping voltammetry procedure by using a glassy carbon electrode as working electrode. Under optimum conditions, the linear range values for Pb2+ and Cd2+ in seawater were 0.2-3.2 μg/L and 0.1-3.2 μg/L, respectively. The concentrations of Pb2+ and Cd2+ in five real samples collected from coastal sites of Qingdao City were determined on site, and the results were in good agreement with that obtained with the atomic absorption spectroscopy method. In addition, the analytical performance of working electrode modified with Bi film by in situ mode was investigated in comparison with that by ex situ mode. The results showed that the in situ mode was much better than the ex situ one.

Characterisation of gold electrodes modified with self-assembled monolayers of l-cysteine for the adsorptive stripping analysis of copper

Electrochemical sensors for copper ions in environmental samples were prepared by modifying gold electrodes with l-cysteine by self-assembly. The adsorption of l-cysteine on gold electrodes was studied by electrochemical reductive desorption in 0.5 M KOH, and the interaction of l-cysteine with copper ions was investigated by cyclic voltammetry, chronoamperometry and X-ray photoelectron spectroscopy. At low concentrations the ratio of l-cysteine to bound Cu(II) is 2:1. At higher concentrations (0.1 M) copper reacts with adsorbed cysteine forming copper sulfide on the electrode surface. On a modified l-cysteine gold electrode, Osteryoung square wave voltammetric determination of Cu(II) with a detection limit below 5 ppb has been demonstrated.

Trace metal speciation in the Pieman River catchment, western Tasmania

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

Influence of chromium content on the dry machining performance of cathodic arc evaporated TiA1N coatings

Physical vapour deposition (PVD) titanium aluminium nitride coated cutting tools are used extensively in global manufacturing for reducing production costs and improving productivity in a number of aggressive metal-cutting operations, namely, dry and high-speed machining. In this investigation, the performance of Ti1−xAlxN and Ti1−x−yAlxCryN coatings was assessed on Co-HSS twist drills used to machine grey cast iron. The failure criterion for drills was defined as a critical sized flank wear land at the outer corners of the drills. Using this criterion, the average tool life of uncoated twist drills was increased by factors of 2.5, 3.0 and 3.0 by Ti0.59Al0.41N, Ti0.27Al0.19Cr0.54N and Ti0.21Al0.14Cr0.65N coatings, respectively. Notwithstanding the similar increase in average tool life, the Ti1−x−yAlxCryN coatings produced more consistent results than the Ti1−xAlxN coated drills with standard deviations of 67, 3 and 19 holes, respectively. This result has significant practical implications in manufacturing, since drills are not replaced on an individual basis, but rather on a preset tool change frequency. The present paper discusses the performance of Ti1−xAlxN and Ti1−x−yAlxCryN coated drills in terms of average and practical drill life and concludes with remarks on the characterisation of PVD coatings and their significance on the performance of Co-HSS twist drills when dry machining grey cast iron.

Reducing the macroparticle content of cathodic arc evaporated TiN coatings

Cathodic arc evaporation (CAE) is a widely used technique for generating highly ionised plasma from which hard, wear-resistant PVD coatings can be deposited. A major drawback of this technique is the emission of micrometer-sized droplets of cathode material from the arc spot, which are commonly referred to as ‘macroparticles’. In this study, the effect of cathode poisoning was investigated as a method to reduce the number of macroparticles in PVD coatings. While the study focuses on the reduction of macroparticles in titanium nitride coatings, the outcomes and key findings can be broadly applied to the cathodic arc process, in particular, for the reduction of macroparticles in more advanced CAE coatings. The results support earlier findings that have shown that poisoning of the cathode can reduce the number of macroparticles emitted from the arc spot. The results of glow discharge optical emission spectroscopy (GD-OES) showed that the titanium content of the coatings varied little between the respective coatings despite changes in the deposition pressure from 0.1 to 1.2 Pa. The GD-OES results also showed the presence of oxide contamination at the surface of the coatings, which was significantly reduced with increasing deposition pressure. The coatings were also deposited onto high-speed steel twist drills to compare the metal-cutting performance when dry drilling a workpiece of cast iron. The results of the drill tests showed that tool life increased with a reduction in the number of macroparticles.

Adsorption and voltammetry of butyltin compounds

The adsorption of tributyltin onto materials commonly used for the construction of sampling and analytical equipment from aqueous solutions of varying ionic composition has been examined. The adsorption appears to be controlled by non-polar interactions between tributyltin and the surface involved. Since the speciation and hence polarity of tributyltin is affected by the ionic composition of the medium, the extent of adsorption is affected by the salinity and pH of a sample. The adsorption is rapid and, unless strategies are adopted to eliminate its effects, may render analytical results invalid. The electrochemistry of tributyltin, dibutyltin and monobutyltin, individually and in mixtures, has been investigated in aqueous media at mercury electrodes. The basic electrochemistry of each compound is summarised by the reaction BunSn (4-n)+ + (4-n)e- right left harpoons BunSn where n is the number of butyl groups attached to the tin atom. However, the electrochemistry of each compound is largely confined to the surface of the mercury electrode, and the simplicity of the above reaction is disrupted by polymerisation reactions and by butyl exchange processes occurring with the mercury electrode. When mixtures of butyltin compounds are present, the various processes that occur for each individual compound interfere with each other. A direct voltaminetric method for the determination of butyltin compounds in natural waters is therefore probably not possible.

Improved cathodic disbondment performance of polyethylene blends

Cathodic disbondment (CD) performance of a range of modified polyethylenes (PE) compression molded on to steel plates at 320[degrees]C is reported. Adhesion strength was measured by the 90[degrees] peel test and good dry adhesion strength was obtained for all modified polyethylene materials and blends, as well as for the neat polymer. It is shown that dry bond strength does not correlate with CD performance. Initial results of wet peel tests of samples in various concentrations of NaOH are presented where it is observed that for samples with improved wet adhesion strength, CD performance was also Improved. Surface polarity was determined from contact angle measurements, and it is shown that increased surface polarity of the coating was not the only determinant for improved CD performance. Inorganic fillers such as talc were also found to improve CD performance by changing the bulk properties, with little measurable change in polarity. Some mechanistic aspects of CD performance are also discussed.

Modification of thermoplastic coatings for improved cathodic disbondment performance on a steel substrate : a study on failure mechanisms

The effect of blending two different materials with a medium density polyethylene for use as pipe coatings is presented. The influence of such blending on properties such as cathodic disbondment (CD) and wet adhesion on steel is investigated. The components blended include a functionalised polyethylene (PE) containing the polar functionality, maleic anhydride (MAH) and an amorphous elastomer, ethylene-propylene-diene terpolymer (EPDM). It was found that modification of PE with small amount (2.5–3 wt%) of either blended MAH-g-PE or EPDM resulted in a significant improvement in CD performance and wet adhesion strength. The mode of failure and disbondment mechanism was investigated using energy dispersive X-ray spectroscopy (EDXS) and X-ray photoelectron spectroscopy (XPS). The greater resistance of migration of sodium ions increases with the incorporation of the modifiers, and it is proposed that this results in an increase in CD performance.