Simultaneous measurements of Cr, Cd, Hg and Pb species in ng L-1 levels by interfacing high performance liquid chromatography and inductively coupled plasma mass spectrometry

Toxicity, mobility, bioavailability and biofunctions of chromium, cadmium, mercury and lead are heavily dependent upon their specific chemical forms, leading to a high demand to metal speciation analysis rather than total quantification. Simultaneous speciation analysis of multiple metal(loid)s is attractive to a large sample capacity containing unstable analytes due to its economic and environmental advantages over the conventional single elemental strategies. In this work, an analytical method integrating online solid phase extraction into high performance liquid chromatography interfaced with inductively coupled plasma mass spectrometry (ICP-MS) to simultaneously preconcentrate and quantify Cr, Cd, Hg and Pb forms in pg L-1 levels in water was developed. Cr (III + VI), Cd(II), Hg(II), Pb(II), methylmercury (MeHg), ethylmercury (EtHg), and trimethyl (TML) and triethyl lead (TEL) were captured by the C18 adsorbent (equilibrated with 10 mL of 1.0 mM 2-hydroxyethanethiol at 10 mL min-1) and eluted by mobile phase (5.0 mM Cys at pH 2.0), then completely separated on the C18 column within 8.0 min and eventually determined by ICP-MS. Low limits of detection (0.001-0.007 ng L-1) and quantification (0.003-0.023 ng L-1), good relative standard deviations (<4%) and high enrichment factors (827-2656 folds) were obtained with good linearities. Three reference materials of total cadmium (GBW08602), total mercury (GBW08603) and total lead (GBW08601) in water were analyzed by the developed method to validate the accuracy with good agreement with certified values and satisfactory recoveries (92-100%). This method was proved feasible by the determination of Cr, Cd, Hg and Pb compounds in drinking water, river water, pond water and tap water.

Automated summary

In this study, an analytical method integrating online solid phase extraction with high-performance liquid chromatography and inductively coupled plasma mass spectrometry (ICP-MS) was developed to simultaneously preconcentrate and quantify forms of Cr, Cd, Hg, and Pb in water. The method showed low limits of detection, good linearities, and low variability, and was validated by analyzing reference materials and real water samples.