Characterization of volcanic ash nanoparticles and study of their fate in aqueous medium by asymmetric flow field-flow fractionation-multi-detection.

Dimensional and elemental characterization of environmental nanoparticles is a challenging task that requires the use of a set of complementary analytical methods. Asymmetric flow field-flow fractionation coupled with UV-Vis, multi-angle laser light scattering and ICP-MS detection was applied to study the nanoparticle fraction of a volcanic ash sample, in a Milli-Q water suspension at pH 6.8. It has been shown that the separated by sedimentation nanoparticle fraction of the Klyuchevskoy volcano ash suspension contains 3 polydisperse populations for which size ranges (expressed in gyration radius, rG), hydrodynamic behaviours (evaluated via shape index) and elemental compositions are different. These 3 populations did not dissolve over the 72-h study but aggregated and settled out differently. Thus, the population of particles with gyration radii <140 nm (P1), which contained 6% AlO and represented approximately 20% by mass of the nanoparticle fraction, remained in suspension without observable aggregation. The populations P2 and P3, which represented 67% and 13% by mass in the initial suspension, covered the rG range 25-250 nm and contained 17% and 15% AlO, respectively. Over time, populations P2 and P3 aggregated and their concentration in suspension at 72 h decreased by approximately 40% compared with the initial suspension. The decrease of these nanoparticle populations occurred either from the beginning of the temporal monitoring (P2) or after 30 h (P3). Aggregation generated a new population (P4) in suspension with rG up to 300 nm and mostly consisting of P2. This population represented only up to 6 to 7% of the nanoparticle fraction and decreased beyond 50 h. As a result, the trace elements present in the nanoparticle fraction and monitored (Cu and La) were also no longer found in the suspension. The results obtained can offer additional insights into the fate of volcanic ash nanoparticles in the environment.