Preparation of novel bifunctionalized magnetic nanoparticles for sequential speciation analysis of inorganic arsenic

Abstract

An amino- and mercapto-bifunctionalized magnetic nanocomposite (SMNPs-(NH2 + SH)) was synthesized by modification of silica-coated magnetic nanoparticles (SMNPs) via one-pot co-condensation of 3-aminopropyltriethoxysilane (APTES) and 3-mercaptopropyltrimethoxysilane (MPTMS) for the first time. The bifunctional magnetic nanomaterial was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry, X-ray photoelectric spectroscopy, elemental analysis, thermogravimetric analysis and vibrating sample magnetometry, etc. The prepared SMNPs-(NH2 + SH) nanocomposite was employed as magnetic solid-phase extraction (MSPE) sorbent for speciation of inorganic arsenic without any pre-oxidation or pre-reduction process. Different optimal conditions for the MSPE including sample solution pH and volume, adsorbent amount, loading time, eluent composition and volume, and elution time were investigated systematically. As(V) and As(III) were adsorbed simultaneously at pH 4.0, and then desorbed sequentially by 3 % (v/v) HNO3 and 3 % (v/v) HNO3 with 4 % (m/v) mercaptosuccinic acid followed by inductively coupled plasma-mass spectrometry (ICP-MS) analysis with the limits of detection of 15.2 and 24.5 ng/L respectively at an enrichment factor of 10 fold. The reliability of the stepwise speciation strategy based on SMNPs-(NH2 + SH) was validated by analyzing inorganic arsenic species in certified reference material of environmental water as well as mixed standard solutions of As(V) and As(III), and the results were in good accordance with the certified or standard values. The applicability of the SMNPs-(NH2 + SH)-MSPE-ICP-MS method for speciation analysis of inorganic arsenic was evaluated in spiked tap, rain, lake and river water samples at the recoveries of 92 %–102 % and 92 %–100 % with the relative standard deviations of 3.6 %–7.4 % and 2.3 %–8.2 % for As(V) and As(III) respectively. In consideration of the merits of single adsorbent, facile preparation, easy operation and no invasion to labile inorganic arsenic, the bifunctional material based MSPE protocol is attractive for speciation analysis of arsenic in real environmental samples.