Collective Ion-Pair Single-Drop Microextraction Attenuated Total Reflectance Fourier Transform Infrared Spectroscopic Determination of Perchlorate in Bioenvironmental Samples.

Perchlorate (ClO4-) is an environmental pollutant that affects human health. Perchlorate acts as a competitive inhibitor of iodine uptake in the thyroid gland (sodium-iodide symporter inhibitor); thus, its determination is important for public health concerns. Water and milk constitute a significant portion of the human diet. Because regular intake leads to an increase in perchlorate concentration in the human body, the estimation of perchlorate is of great concern. In this work, ion-pair single-drop microextraction (SDME) combined with attenuated total reflectance (ATR)-FTIR spectroscopy has been developed for the determination of perchlorate in bioenvironmental (soil, water, dairy milk, breast milk, and urine) samples. Perchlorate was extracted in a single drop of methyl isobutyl ketone as an - with the cationic surfactant cetyltrimethylammonuim bromide under optimized conditions. The strongest IR peak (at 1076 cm-1) was selected for the quantification of perchlorate among three observed vibrational peaks. Eight calibration curves for different concentration ranges of perchlorate were prepared, and excellent linearity was observed for absorbance and peak area in the range of 0.03-100 ng/mL perchlorate, with r values of 0.977 and 0.976, respectively. The RSDs (n = 8) for the perchlorate concentration ranges of 0.03-100, 0.03-0.5, 0.5-10, and 10-100 ng/mL were in the range of 1.9-2.7% for the above calibration curves. The LOD and LOQ in the present work were 0.003 and 0.02 ng/mL, respectively. The extracted microdrop was analyzed directly by ATR-FTIR spectroscopy. The parameters affecting SDME, i.e, effect of pH, stirring rate, reagent concentration, microdrop volume, and extraction time, were optimized, and the role of foreign species was also investigated. F- and t-tests were performed to check the analytical QA of the method. A noteworthy feature of the reported method is the noninterference of any of the associated ions. The results were compared with those of the ion chromatography MS method, and a high degree of acceptability was found. The method was successfully applied for the determination of perchlorate in bioenvironmental samples.