Analysis of perchlorate in human saliva by liquid chromatography-tandem mass spectrometry

Perchlorate is both a naturally occurring anion and the disassociated anion of manufactured perchlorate salts. Because perchlorate has the abilityto blockthe uptake of iodide bythe thyroid gland, it is considered a potent thyroid hormone disruptor in humans. Methods for the analysis of perchlorate in biological matrices are needed to enable assessment of exposures and to elucidate adverse health outcomes. This study describes a method for the analysis of perchlorate in human saliva samples, using a simple dilution and ultrafiltration technique. Quantification of perchlorate in saliva samples using isotopically labeled standards (Cl18O4) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) offers great selectivity and sensitivity. Matrix effects in perchlorate analysis are compensated by spiking of saliva samples with an isotopically labeled internal standard for perchlorate. The LC-MS/MS calibration was found to be linear over the range from 0.01 to 50 ng/mL for 100 microL injections (i.e., 1-5000 pg injection). Fortified blank and matrix spike recoveries were between 93% and 97%, when spiked at a 2 ng/mL level. Relative standard deviations (RSDs) of daily calibration checks and fortified blanks were < or =10%. The relative percent difference, in laboratory duplicate analysis of original samples, was less than 1%. The method quantitation limit (LOQ) was determined to be 0.4 ng/mL, which includes a sample dilution factor. Salivary concentrations of a convenience sample of 83 persons working and/or living in Albany County of New York State ranged from 0.4 to 37 ng/mL with a mean concentration of 5.3 ng/mL Including sample preparation steps, 25 samples can be analyzed within 8 h. This selective and rapid method for analysis of perchlorate in human saliva will enable investigators and scientists to determine the extent of an individual's perchlorate exposure and, potentially, the compound's effects on human health. Analysis of perchlorate in saliva from a population (n = 86) with no major sources of exposures, using the method developed in this study, suggests the ubiquitous occurrence of this compound in saliva.