Assessing the aggregation behaviour of iron oxide nanoparticles under relevant environmental conditions using a multi-method approach

Iron nanoparticles are becoming increasingly popular for the treatment of contaminated soil and groundwater; however, their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Assessing their stability under environmental conditions is crucial for determining their environmental fate. A multi-method approach (including different size-measurement techniques and the DLVO theory) was used to thoroughly characterise the behaviour of iron oxide nanoparticles (Fe₂O₃NPs) under environmentally relevant conditions. Although recent studies have demonstrated the importance of using a multi-method approach when characterising nanoparticles, the majority of current studies continue to use a single-method approach.Under some soil conditions (i.e. pH 7, 10 mM NaCl and 2 mM CaCl₂) and increasing particle concentration, Fe₂O₃NPs underwent extensive aggregation to form large aggregates (>1 μm). Coating the nanoparticles with dissolved organic matter (DOM) was investigated as an alternative “green” solution to overcoming the aggregation issue instead of using the more commonly proposed polyelectrolytes. At high concentrations, DOM effectively covered the surface of the Fe₂O₃NPs, thereby conferring negative surface charge on the particles across a wide range of pH values. This provided electrostatic stabilisation and considerably reduced the particle aggregation effect. DOM-coated Fe₂O₃NPs also proved to be more stable under high ionic strength conditions. The presence of CaCl₂, however, even at low concentrations, induced the aggregation of DOM-coated Fe₂O₃NPs, mainly via charge neutralisation and bridging. This has significant implications in regards to the reactivity and fate of these materials in the environment.