Biogeochemially reactive inorganic mercury (RHg) is an important fraction of Hg. Researchers have attempted to measure RHg when characterizing Hg-impacted sites, conducting research and development of remediation practices, or evaluating remediation efficiency. In these uses, RHg will be the best choice for analysis in ways that total methyl, and other species of Hg cannot duplicate. The fraction has been inadequately measured using the Sn 2+ reduction method and operationally defined as "Sn 2+ reducible Hg 2+ ", but the resulting data did not reflect well the nature of the fraction and caused researchers to lose interest, thus limiting the use of RHg in past years. In this work, the problems of using the Sn 2+ reduction method were discovered to be generating irreproducible and negatively biased results. Negative bias from 20% to 99% was found in different types of waters. To obtain reliable results, an ethylation-based GC-CVAFS method was used to determine RHg. The performance of the method was evaluated by comparing it to the Sn 2+ reduction method. Biogeochemically meaningful results have been obtained in the application of the method to determine RHg in mercury mine-impacted waters from the Idrijca River in Slovenia.