A pH-dependent CT sensitive method for detection of trace Mn in milk by UV-spectrophotometry

Abstract

In this study, a new method was developed for the extractive pre-concentration/detection of trace Mn in milk prior to analysis by UV-spectrophotometry. The method is based on the pH-controlled intra-ligand charge transfer (ICT) complexation of modifier, 2-HBT in presence of trace Mn (II), and then the extraction of the complexes, where the hydrazine and hydrazone tautomers are predominant at pHs of 2.0/ 3.0, and pH 6.0 because of CT at pH 4.0. The free Mn (II) and total Mn levels of the samples were detected at 269 nm by UV-spectrophotometry. For total Mn, the method was validated by analysis of two certified milk samples. The results were statistically in good agreement with the certified values, and the precision was lower than 6.4%. After a pre-concentration of 62.5-fold, the limits of detection were 1.45/1.92 and 1.54/2.12 μg L−1 in range of 5–165 and 5–150 µg L−1 from the solvent-based and matrix-matched calibration curves, respectively. There is not a matrix effect from comparison of the calibration curves’s slopes. The method was successfully applied to analysis of milk samples. In terms of speciation, the free Mn (II) and total Mn levels in milk were in the range of 7.65–30.4 μg L−1, and 10.2–34.7 and 10.7–35.5 μg L−1 after the microwave and ultrasound assisted extraction.