Removal of inorganic mercury by selective extraction and coprecipitation for determination of methylmercury in mercury-contaminated soils by chemical vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)

A procedure is developed for selective extraction of methylmercury (CH₃Hg⁺) from heavily Hg-contaminated soils and sediments for determination by chemical vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS). Soils artificially contaminated with 40 μg g^-1 inorganic mercury (Hg²⁺) or methylmercury chloride (CH₃HgCl) were agitated by shaking or exposing to ultrasounds in dilute hydrochloric acid (HCl) or nitric acid (HNO₃) solutions at room temperature. Extractions in HCl (5 or 10% v/v) resulted in substantial leaching of Hg²⁺ from soils, whereas 5% (v/v) HNO₃ provided selectivity for quantitative extraction of CH₃Hg⁺ with minimum Hg²⁺ leaching. Agitation with ultrasounds in 5% (v/v) HNO₃ for about 3 min was sufficient for extraction of all CH₃Hg⁺ from soils. Coprecipitations with Fe(OH)₃, Bi(OH)₃ and HgS were investigated for removal of residual Hg²⁺ in soil extracts. Hydroxide precipitations were not effective. Thiourea or l-cysteine added to soil extracts prior to hydroxide precipitation improved precipitation of Hg²⁺, but also resulted in removal of CH₃Hg⁺. HgS precipitation was made with dilute ammonium sulfide solution, (NH₄)₂S. Adding 30 μL of 0.35 mol L^-1 (NH₄)₂S to soil extracts in 5% (v/v) HNO₃ resulted in removal of all residual Hg²⁺ without impacting CH₃Hg⁺ levels. Vapor generation was carried out by reacting Hg²⁺-free soil extracts with 1% (m/v) NaBH₄. No significant interferences were observed from (NH₄)₂S on the vapor generation from CH₃Hg⁺. The slopes of the calibration curves for CH₃HgCl standard solutions in 5% (v/v) HNO₃ with and without (NH₄)₂S were similar. Limits of detection (LOD, 3s method) were around 0.08 μg L^-1 for 5% (v/v) HNO₃ blanks (n = 10) and 0.10 μg L^-1 for 5% (v/v) HNO₃ + 0.005 mol L^-1 (NH₄)₂S blanks (n = 10). Percent relative standard deviation (%RSD) for five replicate measurements varied between 3.1% and 6.4% at 1.0 CH₃HgCl level. The method is validated by analysis of two certified reference materials (CRM); purely Methylmercury sediment (SQC1238, 10.00 ± 0.291 ng g^-1 CH₃Hg⁺) and Hg-contaminated Estuarine sediment (ERM - CC580, 75 ± 4 ng g^-1 CH₃Hg⁺ and 132 ± 3 μg g^-1 total Hg). CH₃Hg⁺ values for SQC1238 were between 13.0 and 13.2 ng g^-1, and 79 and 81 ng g^-1 for ERM - CC580. Hg-contaminated soils (57-96 μg g^-1 total Hg) collected from the floodplains of Oak Ridge, TN were analyzed for CH₃Hg⁺ using the procedure by CVG-ICPMS. CH₃Hg⁺ levels ranged from 30 to 51 ng g^-1 and did not correlate with total Hg levels (R² = 0.01).