Method development for determination of trace amounts of palladium in environmental water samples by ICP-MS/MS after pre-concentration on thiol-functionalized MCM-41 materials.

The anthropogenic cycle of Pd in the environment, its fate and impact is still unknown due to limitations of measurement techniques. For separation and pre-concentration of Pd(II) ions, mesoporous silica materials MCM-41 were synthesized and functionalized with different amounts of 3-mercaptopropyltrimethoxysilane (MPTMS) by co-condensation and grafting methods. The structural and textural properties of materials were characterized using XRD, TEM, SEM and BET techniques. The results proved that functionalization with thiol groups did not significantly affect structural and textural parameters of synthesized sorbents. The Pd(II) ions were quantitatively retained on sorbents functionalized by grafting in acidic solutions (pH 2), efficiently eluted with 0.1 mol L thiourea solution in 1 mol L HCl and determined by electrothermal atomic absorption spectrometry (ETAAS). The limit of detection (LOD) of the developed SPE ETAAS method was 0.06 ng mL, and the pre-concentration factor was 30. For analysis of Pd in environmental water samples inductively coupled plasma mass spectrometry (ICP-MS) in MS/MS mode was used. Spectral interferences on Pd caused by the presence of Sr in water samples were eliminated using helium (5 mL min) or ammonia (7 mL min) gas in collision/reaction cell. The developed SPE ICP-MS method is characterized by good selectivity in the presence of interfering elements and chloride ions and detection limit of 0.0002 ng mL. Its accuracy was confirmed by analysis of spiked water samples. The application of ICP-MS together with efficient separation/pre-concentration of analyte on thiol-functionalized MCM-41 sorbents allows to determine Pd in environmental water samples at pg mL level.