Macronutrient and PFOS bioavailability manipulated by aeration-driven rhizospheric organic nanocapsular assembly

Ubiquitous presence of the extremely persistent pollutants, per- and polyfluoroalkyl substances, is drawing ever-increasing concerns for their high eco-environmental risks which, however, are insufficiently considered based on the assembly characteristics of those amphiphilic molecules in environment. This study investigated the re-organization and self-assembly of perfluorooctane sulfonate (PFOS) and macronutrient molecules from rhizospheric organic (RhO) matter induced with a common operation of aeration. Atomic force microscopy (AFM) with infrared spectroscopy (IR)-mapping clearly showed that, after aeration and stabilization, RhO nanocapsules (∼ 1000 nm or smaller) with a core of PFOS-protein complexes coated by "lipid-carbohydrate" layers were observed whereas the capsule structure with a lipid core surrounded by "protein-carbohydrate-protein" multilayers was obtained in the absence of PFOS. It is aeration that exerted the disassociation of pristine RhO components, after which the environmental concentration PFOS restructured the self-assembly structure in a conspicuous "disorder-to-order" transition. AFM IR-mapping analysis of faeces combined with quantification of component uptake denoted the decreased ingestion and utilization of both PFOS and proteins compared with lipids and carbohydrates when Daphnia magna were fed with RhO nanocapsules. RhO nanocapsules acted as double-edged swords via simultaneously impeding the bioaccessibility of hazardous PFOS molecules and macronutrient proteins; and the latter might be more significant, which caused a malnutrition status within merely 48 h. Elucidating the assembly structure of natural organic matter and environmental concentration PFOS, the finding of this work could be a crucial supplementation to the high-dose-dependent eco-effect investigations on PFOS.