Methylmercury measurement in whole blood by isotope-dilution GC-ICPMS with 2 sample preparation methods.

BACKGROUND Despite its known toxicity, methylmercury is rarely measured directly in clinical studies; instead, conclusions are based on total mercury measurements. We have developed isotope-dilution-based methods for methylmercury-specific analysis of whole blood by coupled gas chromatography-inductively coupled plasma mass spectrometry (GC-ICPMS). METHODS We analyzed animal and human blood samples after alkaline digestion or extraction of methylmercury into dichloromethane and back extraction into water. Methylmercury was converted to the volatile ethyl derivative, purged, and trapped on a solid-phase collection medium, and then introduced into the GC-ICPMS system. RESULTS Limits of quantification were 0.4 and 0.03 microg/L at a signal-to-noise ratio of 10 with the alkaline digestion and extraction methods, respectively. Extraction met our selected acceptable total error criterion, with an SD of 0.58 microg/L at the critical maternal blood concentration of 5.8 microg/L. Results obtained with alkaline digestion indicated the need for improved random analytical uncertainty, which was achieved by increasing the enrichment of the isotope dilution. For 37 blood samples, the mean (SD) proportion of total mercury present as methylmercury was 60 (27)%, range 6%-100%. CONCLUSIONS The combination of extraction and isotope-dilution GC-ICPMS meets the requirements for use as a reference method for measuring methylmercury in whole blood.