Determination of trace metal speciation parameters by using screen-printed electrodes in stripping chronopotentiometry without deaerating.

The objective of this study was to exploit the advantages of stripping chronopotentiometry (SCP) and stripping chronopotentiometry at scanned deposition potential (SSCP) for trace metal speciation analyses by using thin-film mercury screen-printed electrodes (TMF-SPE). At first, the SCP parameters were optimised for TMF-SPE, in order to reach the complete depletion regime. It has been shown that a stripping current higher than or equal to 10 µA allows this regime to be attained without removing oxygen from the solution. Then, these analytical conditions were used for the construction of SSCP curves for Cd-PDCA and Cd-NTA. When the concentration of free ligand in solution was known, the knowledge of the model describing the SSCP curves in absence and presence of a complex and the use of an effective fitting tool enabled estimating the stability constant and the rate constants for complexation. Further studies with complexes of restricted mobility are however necessary to assess the usefulness of this procedure to also estimate the diffusion coefficient of the complexes. Besides, this study showed that this approach was valid even when ligands were not in excess at the electrode during stripping.

Development of analytical procedures for the determination of hexavalent chromium in corrosion prevention coatings used in the automotive industry.

The European directive 2000/53/EC limits the use of Cr(VI) in vehicle manufacturing. Although a maximum of 2 g of Cr(VI) was authorised per vehicle for corrosion prevention coatings of key components, since July 2007 its use has been prohibited except for some particular applications. Therefore, the objective of this work was to develop direct analytical procedures for Cr(VI) determination in the different steel coatings used for screws. Instead of working directly with screws, the optimisation of the procedures was carried out with metallic plates homogeneously coated to improve the data comparability. Extraction of Cr(VI) from the metallic parts was performed by sonication. Two extraction solutions were tested: a direct water extraction solution used in standard protocols and an ammonium/ammonia buffer solution at pH 8.9. The extracts were further analysed for Cr speciation by high-performance liquid chromatography (HPLC) inductively coupled plasma (ICP) atomic emission spectrometry or HPLC ICP mass spectrometry depending on the concentration level. When possible, the coatings were also directly analysed by solid speciation techniques (X-ray photoelectron spectroscopy, XPS, and X-ray absorption near-edge structure, XANES) for validation of the results. Very good results between the different analytical approaches were obtained for the sample of coating made up of a heated paint containing Zn, Al and Cr when using the extracting buffer solution at pH 8.9. After a repeated four-step extraction procedure on the same portion test, taking into account the depth of the surface layer reached, good agreement with XPS and XANES results was obtained. In contrast, for the coatings composed of an alkaline Zn layer where Cr(VI) and Cr(III) are deposited, only the extraction procedure using water allowed the detection of Cr(VI). To elucidate the Cr(VI) reduction during extraction at pH 8.9, the reactivity of Cr(VI) towards different species of Zn generally present in the coatings (metallic Zn and zinc oxide) was studied. The results showed that metallic Zn rapidly reduces Cr(VI), whereas this reaction is less evident in the presence of zinc oxide. Water was then retained for coatings containing metallic Zn.

Ferrate(VI) oxidation of cyanide in water.

Experiments were conducted to test removal of cyanide (free cyanide and several cyanide complexes) in water, under alkaline medium (pH > or = 11), by a new potassium ferrate salt. The removal rate of free cyanide by oxidation with Fe(VI) was greater at pH 11.0 than at pH 12.0. A complete oxidation was obtained with a 2.67 Fe(VI)/CN ratio at pH 11.0. In these conditions, the rate of cyanide oxidation by Fe(VI) was slow, with a reaction rate constant estimated at 0.95 +/- 0.10 s(-1) l mol(-1) at pH 11.0 and 19.6 degrees C in this study. This study revealed that Fe(VI) did not decompose all cyanide complexes. Copper, cadmium and zinc complexes were removed efficiently by Fe(VI). Moreover, these metals were also removed from the solution by coagulation effect of Fe(OH)3, the Fe(VI) product of reaction. A particular behaviour was reported with copper, as a rapid oxidation of cyanide was observed in the presence of this metal. On the contrary, oxidation of nickel and silver complexes was incomplete.

Development of analytical procedures for determination of total chromium by quadrupole ICP-MS and high-resolution ICP-MS, and hexavalent chromium by HPLC-ICP-MS, in different materials used in the automotive industry.

A European directive was recently adopted limiting the use of hazardous substances such as Pb, Hg, Cd, and Cr(VI) in vehicle manufacturing. From July 2003 a maximum of 2 g Cr(VI) will be authorised per vehicle in corrosion-preventing coatings of key components. As no standardised procedures are available to check if produced vehicles are in agreement with this directive, the objective of this work was to develop analytical procedures for total chromium and Cr(VI) determination in these materials. The first step of this study was to optimise digestion procedures for total chromium determination in plastic and metallic materials by inductively coupled plasma mass spectrometry (ICP-MS). High resolution (HR) ICP-MS was used to examine the influence of polyatomic interferences on the detection of the (52)Cr(+) and (53)Cr(+) isotopes. If there was strong interference with m/ z 52 for plastic materials, it was possible to use quadrupole ICP-MS for m/ z 53 if digestions were performed with HNO(3)+H(2)O(2). This mixture was also necessary for digestion of chromium from metallic materials. Extraction procedures in alkaline medium (NH(4)(+)/NH(3) buffer solution at pH 8.9) assisted by sonication were developed for determining Cr(VI) in four different corrosion-preventing coatings by HPLC-ICP-MS. After optimisation and validation with the only solid reference material certified for its Cr(VI) content (BCR 545; welding dusts), the efficiency of this extraction procedure for screw coatings was compared with that described in the EN ISO 3613 standard generally used in routine laboratories. For coatings comprising zinc and aluminium passivated in depth with chromium oxides the extraction procedure developed herein enabled determination of higher Cr(VI) concentrations. This was also observed for the screw covered with a chromium passivant layer on zinc-nickel. For coating comprising a chromium passivant layer on alkaline zinc the standardized extraction procedure was more efficient. In the case of painted metallic plate, because of a reactive matrix towards Cr(VI), its extraction without degradation was difficult to perform.

Solubility and disintegration of zinc phosphate cement.

The mechanism of erosion of a zinc phosphate cement was studied using two experimental procedures: discs of dental cement were immersed in distilled water under unrenewed conditions as defined by ISO standard; or discs were immersed under continuously running distilled water to simulate the oral environment. Both experiments revealed no physical disintegration mechanism, and suggest that erosion is only controlled by dissolution.