A bi-parametric sequential injection method for the determination of copper(II) and zinc(II) when present together in aqueous samples was developed. This was achieved by using a non-specific colorimetric reagent (4-(2-pyridylazo)resorcinol, PAR) together with two ion-exchange polymeric materials to discriminate between the two metal ions. A polymer inclusion membrane (PIM) and a chelating resin (Chelex 100) were the chosen materials to retain zinc(II) and copper(II), respectively. The influence of the flow system parameters, such as composition of the reagent solutions, flow rates and standard/sample volume, on the method sensitivity were studied. The interference of several common metal ions was assessed, and no significant interferences were observed (<10% signal deviation). The limits of detection were 3.1 and 5.6 µg L−1 for copper(II) and zinc(II), respectively; the dynamic working range was from 10 to 40 µg L−1 for both analytes. The newly developed sequential injection analysis (SIA) system was applied to natural waters and soil leachates, and the results were in agreement with those obtained with the reference procedure.
A flow-based method for the spectrophotometric determination of chromium (VI) in recreational waters with different salinities was developed. Chromium can occur in the environment in different oxidation states with different related physiological properties. With regard to chromium, the speciation is particularly important, as the hexavalent chromium is considered to be carcinogenic. To achieve that purpose, the use of the diphenylcarbazide (DPC) selective colored reaction with the hexavalent chromium was the chosen strategy. The main objective was to develop a direct and simple spectrophotometric method that could cope with the analysis of different types of environmental waters, within different salinity ranges (fresh to marine waters). The potential interference of metal ions, that can usually be present in environmental waters, was assessed and no significant interferences were observed (<10%). For a complete Cr(VI) determination (three replicas) cycle, the corresponding reagents consumption was 75 µg of DPC, 9 mg of ethanol and 54 mg of sulfuric acid. Each cycle takes about 5 min, including the system clean-up. The limit of detection was 6.9 and 12.2 µg L−1 for waters with low and high salt content, respectively. The method was applied for the quantification of chromium (VI) in both fresh and marine water, and the results were in agreement with the reference procedure.
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