Solid phase microextraction speciation analysis of triclosan in aqueous media containing sorbing nanoparticles

Environmental context Speciation analysis of organic compounds in aquatic media is often performed using solid phase microextraction with the assumption that only the free organic form is accumulated. We show that in the presence of silica nanoparticles, this interpretation is confounded by partitioning of nanoparticulate-bound compounds between water and the solid phase, as well as their aggregation at solid–bulk medium interfaces. Equilibrium measurement of the target analyte is feasible if the solid phase is protected by a suitable membrane. Abstract Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid phase poly(dimethylsiloxane) (PDMS). Furthermore, they appear to aggregate at the PDMS–water interface. The total triclosan concentration in the solid phase thus includes both the free and the NP-bound forms. Proper computation of the analyte concentration in the sample medium requires (i) consideration of the speciation of triclosan inside the solid phase and (ii) elimination of the effects of aggregation of NP complexes at the solid phase–bulk medium interface. Possible solutions include application of a protective membrane with pore size smaller than the NP diameter. This allows measurement of the free triclosan concentration, albeit at the cost of longer accumulation times and loss of kinetic information on the triclosan–NP complex.