Determination of trace elements in siliceous samples by ICP-MS after precipitation of silicon as sodium fluorosilicate

Abstract.

A matrix removal procedure has been developed for the determination of trace elements, including As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, Tl, Zn and V, in siliceous materials by inductively coupled plasma mass spectrometry (ICP-MS). Soil and sediment samples were dissolved in a mixture of HNO₃ and HF in sealed vessels by using a microwave oven. Silicon matrix in the solutions was precipitated as sparingly soluble sodium fluorosilicate (Na₂SiF₆) by adding 0.5 mL of 300 mg mL⁻¹ NaCl solution. Simultaneous precipitation of sodium and silicon was achieved in highly acidic solutions containing 30–40% (v/v) HNO₃. A mixture of methanol and nitric acid afforded back-extraction of the trace elements without significant dissolution of the Na₂SiF₆. Samples were analyzed by ICP-MS for trace elements and residual silicon. Calibration was made by aqueous multi-element standard solutions. Up to 95% of the silicon was successfully removed yielding solutions suitable for introduction to ICP-MS. The method was validated by analysis of two NIST certified reference materials; SRM 2711 (Montana Soil) and SRM 2704 (Buffalo River Sediment). Accurate results were obtained for all elements, including those for As, Hg and Se that suffer from losses due to the presence of their volatile species when silicon was converted to volatile SiF₄ via heat-assisted evaporation to dryness. The recoveries from the SRM samples varied between 80% (Cr) and 109% (Hg). No significant interferences were observed from molecular ions of chloride and residual sodium on ⁷⁵As, ⁶³Cu, ⁶⁰Ni, ⁷⁷Se and ⁵¹V.