Gas-Phase Ion Association Provides Increased Selectivity and Sensitivity for Measuring Perchlorate by Mass Spectrometry

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Abstract

Perchlorate (ClO4-) competitively inhibits the uptake of iodide by the thyroid gland. Trace quantities of perchlorate are being increasingly detected in food and environmental samples. There is great concern that perchlorate contamination may be far more widespread than believed until now. Increasingly sensitive and unambiguous methods are needed for measuring perchlorate. We report here an ion chromatography-ion association-electrospray ionization-mass spectrometry (IC/IA-ESI-MS) method of substantially greater selectivity and sensitivity than other available single-stage MS approaches. A long chain dipositive cationic agent (D2+) is added postcolumn in low concentration. This ion associates with perchlorate, even in the gas phase. Perchlorate is, thus, detected as DClO4+ in the positive ion mode at an m/z value between 300 and 400 (depending on the choice of D2+). This results in much better S/N and selectivity, as compared to detecting 35ClO4- at m/z 99, where H34SO4- also responds. We show results for various dicationic agents which vary in their selectivity and affinity for ClO4-, typically being at least 1 order of magnitude more selective for ClO4- over HSO4-. For a 100-microL injected standard, limits of detection (LOD, S/N = 3) are as good as 25 ng/L on a single quadrupole mass spectrometer. Calibration for concentrations up to 100 microg/L displays an r2 value of > or =0.9993. We show applicability to various real samples. A number of the studied reagents are suitable for such applications.

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