Speciation of inorganic and organometallic arsenic in various matrices with a novel SPME fiber functionalized with iron nanoparticles prior to LC-ICP-MS determination.

A novel SPME-LC-ICP-MS methodology is described for the simultaneous microextraction/speciation/determination of the metabolically critical inorganic and organoarsenic species, namely, As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) in natural waters such as drinking and geothermal waters, and biological fluids such as urine. The novelty of the study stems also from the use of home-made SPME fibers for the extraction process, and from the proposed methodology needing no derivatization step. SPME fibers were prepared with in-tube capillary template approach through the immobilization of iron nanoparticles into agarose matrix. The fibers demonstrated reproducible extraction (<10 % RSD), good mechanical strength and good solvent resistivity. The separation of the analytes was realized by HPLC with a strong anion exchange column via gradient elution using different concentrations of (NH₄)₂CO₃ (pH 8.50), and the on-line detection of eluted analytes was achieved by ICP-MS. The validity of the proposed methodology was verified via the analysis of certified reference materials (SRM 1643e, Natural Water-Trace Elements, and SRM 2669, Arsenic Species in Frozen Human Urine) and through spike recovery tests. The values of percentage recovery for SRM 2669 were 90.7 % for As(III), 99.8 % for As(V), 93.6 % for DMA, and 85.9 % for MMA. A good correlation was also found between the certified (60.45 μgL^-1) and determined (59.00 μgL^-1) values for SRM 1643e. Moreover, the speciation capability of the method was demonstrated on various natural waters and biological fluids.