Simultaneous enrichment of inorganic and organic species of lead and mercury in pg L−1 levels by solid phase extraction online combined with high performance liquid chromatography and inductively coupled plasma mass spectrometry

Quantification of ultra-trace inorganic and organic species of lead and mercury in unpolluted environmental water is crucial to estimate the mobility, toxicity and bioavailability and interactions. Simultaneous pre-concentration of Pb and Hg species in pg L −1 levels followed by multi-elemental speciation analysis makes great sense to a large set of unstable samples because of time advantages. Herein simultaneous enrichment and speciation analysis of ultra-trace lead and mercury in water was developed by online solid-phase extraction coupled with high performance liquid chromatography and inductively coupled plasma mass spectrometry (SPE-HPLC-ICP-MS) for this aim. Pb(II), trimethyl lead (TML), triethyl lead (TEL), Hg(II), methylmercury (MeHg) and ethylmercury (EtHg) were baseline separated in 11 min under gradient elution using 5 mM l -cysteine (Cys) at pH 2.5 in the 0–1 and 4–15 min and 5 mM Cys + 0.5 mM tetrabutyl ammonium hydroxide solution at pH 2.5 in the 1–4 min. Lead and mercury species in 10 mL intact water samples were adsorbed on a 1 cm C 18 enrichment column pre-conditioned with 10 mL of 1 mM 2-mercaptoethanol at 10 mL min −1 , and then directly desorbed by the mobile phases . High enrichment factors (459 for Pb(II), 1248 for TML, 1627 for TEL, 2485 for Hg(II), 1984 for MeHg and 1866 for EtHg) were obtained with good relative standard deviations (<5%), leading to low LODs (0.001–0.011 ng L −1 ) and LOQs (0.004–0.036 ng L −1 ). Good accuracy of this method was validated by two certified reference materials of total lead in water (GBW08601) and total mercury in water (GBW08603) along with spiked recoveries (89–93%). The method was applied to analyze trace lead and mercury species in river, lake, tap and rain water, and purified and mineral water . Inorganic lead of 13–68 ng L −1 and inorganic mercury of 21–49 ng L −1 were measured in the nine water samples whereas TML, TEL and MeHg were not detected with 2–5 ng L −1 EtHg presented only in one river water and tap water .