Development and optimization of a triple quadrupole ICP-MS–based system for the quantification of pre-concentrated gaseous elementary mercury

Understanding the redox reactions and transformation rates of mercury (Hg) species in the environment is important for predicting future gaseous elemental Hg (Hg0) levels and assessing the impacts of anthropogenic Hg0 emissions on human health. Stable Hg isotope tracers are a promising tool for estimating Hg0 production rates; however, traditional analytical approaches for quantifying Hg0, such as atomic fluorescence spectroscopy or atomic absorption spectrometry, cannot differentiate between Hg isotopes, and alternative approaches, such as inductively coupled plasma mass spectrometry (ICP-MS) with a typical aqueous sample introductory system, have relatively higher detection limit of Hg. Here, we developed and evaluated a custom-made thermal desorption unit coupled directly to a triple quadrupole ICP-MS (ICP-QQQ) for the quantification of Hg0 pre-concentrated on Au traps. The performance of the system was validated with measurements of a Hg standard gas and of Hg0 generated from aqueous Hg standards. Using our system, we were able to detect ultra-trace amounts of Hg0 and obtain precise Hg isotope measurements with an analytical error of ≤ 3.5%. Calibration curves with superb linearity (r2 > 0.999) were obtained for the Hg concentration range of 0–300 pg. The method detection limit was approximately 0.01–0.03 pg of Hg. Using the latest ICP-QQQ instrument (Agilent 8900; Agilent Technologies Ltd.) was far superior to using a previous model (Agilent 8800), with the Agilent 8900 showing approximately five times higher sensitivity than the Agilent 8800 as well as the ability to precisely and simultaneously analyze up to five Hg isotopes by time-resolved analysis.