Background: Allergic contact dermatitis to metals is diagnosed by applying a metal salt in a patch test. The bioavailability of the metal salt might depend on the choice of metal salt, the concentration, sweat composition, and pH.
Objectives:The main purpose of this study was to apply chemical speciation modelling, which is based on experimentally derived input data and calculates the concentrations of chemical forms (species) in solutions, to reproduce and discuss clinical patch test results of aluminium and chromium.Methods: Joint Expert Speciation System (JESS), Hydra/Medusa, and Visual MINTEQ were employed to study the bioavailable fraction and chemical form of clinically applied aluminium and chromium salts as a function of salt type, applied concentration, sweat composition, and pH.Results: Investigated aluminium and chromium salts can have a very low bioavailability with a large dependency on sweat composition, pH, metal salt, and concentration.Both aluminium and chromium ions could shift the pH towards acidic or basic values based on their chemical form.Conclusions: Reported seasonal and interpatient variability in positive reactions to aluminium is likely related to sweat pH and composition. Potassium dichromate increases the pH, whereas aluminium and trivalent chromium chloride strongly decrease the pH, possibly increasing skin diffusion.
Copper (Cu) and stainless steel 316L are widely used for biomedical applications, such as intrauterine devices and orthopedic/dental implants. Amino acids are abundantly present in biological environments. We investigated the influence of select amino acids on the corrosion of Cu under naturally aerated and deaerated conditions using a phosphate-free buffer. Amino acids increased the corrosion of Cu under both aeration conditions at pH 7.4. Cu release was also significantly (up to 18-fold) increased in the presence of amino acids, investigated at pH 7.4 and 37°C for 24 h under naturally aerated conditions. Speciation modelling predicted a generally increased solubility of Cu in the presence of amino acids at pH 7.4. 316L, investigated for metal release under similar conditions for comparison, released about 1000-fold lower amounts of metals than did Cu and remained passive with no change in surface oxide composition or thickness. However, amino acids also increased the chromium release (up to 52-fold), significantly for lysine, and the iron release for cysteine, while nickel and molybdenum release remained unaffected. This was not predicted by solution speciation modelling. The surface analysis confirmed the adsorption of amino acids on 316L and, to a lower extent, Cu coupons.
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