Preparation and characterization of a soil reference material from a mercury contaminated site for comparability studies

The preparation and characterization of a soil reference material (SOIL-1) from a site polluted with mercury due to the past mercury mining in Idrija, Slovenia is reported. Homogeneity tests and intercomparison exercises for total (T-Hg) and methylmercury (MeHg) were performed. In addition, selective sequential extraction was applied for Hg fractionation, and multielemental analyses were performed by k0 standardization neutron activation analysis (k0-INAA) and inductively coupled mass spectrometry (ICP-MS) for other trace elements. Comparison of different analytical methods, as well as the distribution of data were critically evaluated using descriptive statistics and analysis of variance (ANOVA). Due to the nugget effect (cinnabar particles representing more than 90% of the mercury), homogeneity for T-Hg determination was difficult to achieve. The intercomparison exercise indicated that in order to obtain comparable results for total mercury (T-Hg) sample decomposition by HF must be performed. These data are then in good agreement with non-destructive methods such as k0-INAA. Accepted reference values calculated taking into account the results obtained by six and three laboratories, respectively, were 67.1±11.3 mg kg−1 for T-Hg and 4.0±1.3 ng g−1 for MeHg (95% confidence intervals). However, the results obtained for Hg fractionation displayed significant differences in the organically bound fraction and elemental Hg. Results obtained by two laboratories using totally different analytical protocols for other elements showed excellent agreement for most elements. In summary, the results obtained for the SOIL-1 sample were of sufficient quality to suggest its use for quality control in laboratories dealing with mercury contaminated soils.