A combination approach using two functionalized magnetic nanoparticles for speciation analysis of inorganic arsenic

Mercapto- and amino-functionalized magnetic nanoparticles, Fe₃O₄@SiO₂@MPTMS (SMNPs-MPTMS) and Fe₃O₄@SiO₂@APTES (SMNPs-APTES), have been applied as magnetic solid-phase extraction (MSPE) sorbents to directly extract arsenite (As(III)) and arsenate (As(V)) respectively, followed by inductively coupled plasma-mass spectrometry (ICP-MS) detection. Various MSPE parameters were optimized including dose of magnetic adsorbent, pH of sample solution, loading and elution conditions of analytes, adsorption capacity and reusability of SMNPs-MPTMS and SMNPs-APTES for As(III) and As(V) respectively. Under the optimized MSPE conditions, this combined scheme possesses excellent selectivity and strong anti-interference ability without any oxidation or reduction prior to capture of these two species. It is found that with a 25-fold enrichment factor, the limits of detection of As(III) and As(V) were 23.5 and 10.5 ng L^-1, respectively. To verify the reliability of the proposed protocol, a certified reference material of environmental water was analyzed, and the results for inorganic arsenic species were in close agreement with the certified values. The applicability of the combination strategy for speciation analysis of inorganic arsenic was evaluated in spiked tap, river, lake and rain water samples. Good recoveries of 89%-96% and 90%-102% were achieved for As(III) and As(V), respectively, with the relative standard deviation ranges of 3.2%-8.0% and 2.5%-7.6%. Through the characterization of functionalized magnetic nanoparticles and the optimization of MSPE experiment, it is confirmed that the existence of mercapto and amino groups on SMNPs-MPTMS and SMNPs-APTES sorbents are responsible for the extraction of As(III) and As(V), respectively, via coordination and electrostatic interactions.