Optimisation of distillation as an isolation method for the determination of low methylmercury concentrations in urine samples

Abstract

Methylmercury (MeHg) speciation in urine requires a robust, reproducible and sensitive technique that enables reliable measurements in limited sample volumes. Conventional MeHg extraction by acid digestion allows for processing of only small amounts of urine digest, making accurate MeHg determination in low-concentration samples virtually impossible. Distillation has been proven as an efficient isolation method with very low detection limits for measuring MeHg in water samples; therefore, in this study, it was optimised for urine samples. Combined with aqueous phase ethylation, purging with nitrogen, preconcentration on Tenax trap, isothermal gas chromatography and cold vapour atomic fluorescence detection, distillation achieved high and repeatable urine spike recoveries of 94% ± 7%. Larger measured aliquot volume led to a significantly lower limit of detection (LOD) for distillation compared with acid digestion (1.1 versus 5.5 pg g−1 urine). Thirty-two general population urine samples were analysed using both methods, and the results were compared. Distillation led to better separation of MeHg from inorganic Hg and the matrix. Good correlation was observed between the results obtained by the two methods for samples with MeHg concentrations above 10 pg g−1 urine (slope = 0.9492, R2 = 0.9879). For samples below this MeHg concentration, distillation was superior, enabling the measurement of MeHg in 9 out of 12 urine samples that were below the LOD of acid digestion. Distillation had significantly lower measurement uncertainty, particularly in the low-concentration samples, where the expanded combined standard uncertainty of the acid digestion method reached as high as 43.2% (k = 2), predominantly owing to poor sample repeatability.