Development of structural equation models to unveil source-sink switches of mid-latitude soils for semi-volatile banned pesticides.

A variety of semi-volatile banned pesticides (SVBPs) are ubiquitous in soils of mid-latitude regions. SVBPs undertake complicated soil-gas exchange processes in mid-latitude regions, challenging the understanding of source or sink roles of soils for the semi-volatile contaminants. Herein, we develop structural equation models (SEMs) to unveil source or sink roles of mid-latitude soils (Liaoning, China) in winter and summer for 12 SVBPs (7 organochlorine and 5 organophosphorus pesticides). The 12 SVBPs exhibit different distribution patterns in soils, dependent of sampling seasons, soil characteristics, topographic/climate conditions of soil sites and chemical properties of compounds. SEM Model I (winter) and Model II (summer) reveal the distribution patterns of SVBPs in soils over season changes, indicating sink-source switches of soils for SVBPS from winter to summer. In winter, soil is a sink of 12 SVBPs in the study area, associated with the inputs of SVBPs in soils by air-particulate partition and dry depositions. However, in summer, soil is mainly a source of the same contaminants, mainly through the volatilization and leaching of SVBPs in soils. The sink-source switches of soils for SVBPs are usually dependent of chemical properties of compounds to higher extents than soil characteristics and topographic/climate conditions of soil sites, though these parameters pose different influences in winter and summer. It has been revealed that soil acts as a sink of SVBPs in winter, associated with the inputs of SVBPs in soils by air-particulate partition and dry depositions, whereas soil acts as a source of SVBPs in summer, mainly through the volatilization and leaching of SVBPs in soils. This finding may provide new insights into the unique distribution patterns of SVBPs in soils in mid-latitude regions.

Recyclable Capture and Destruction of Aqueous Micropollutants Using the Molecule-Specific Cavity of Cyclodextrin Polymer Coupled with KMnO4 Oxidation.

The removal of aqueous micropollutants remains challenging because of the interference of natural water constituents that are typically 3-9 orders of magnitude more concentrated. Cyclodextrins, which feature molecular recognition and are widely applied in separation and catalysis, are promising materials in the development of pollutant treatment technologies. Here, we described the facile integration of cyclodextrin polymer (CDP) adsorption and KMnO4 oxidation for recyclable capture and destruction of aqueous micropollutants (i.e., antibiotics and TBBPA). CDP exhibited adsorption efficiencies of 0.81-88% and 0.81-94% toward 14 pollutants at 50.0 ng/L and 50.0 µg/L, respectively, at a solid-to-liquid ratio of 1:1250. The presence of simulated or natural water constituents (e.g., Mg(2+), Ca(2+), DOC, and a combination thereof) did not decrease the adsorption potential of CDP toward these pollutants because the pollutants, based on molecular specificity, were entrapped in the CD cavity. Subsequent KMnO4 oxidation completely degraded the retained pollutants, demonstrating that the pollutants could be broken down in the cavity. Pristine CDP was rearranged into the structurally loose composites that featured a porous CDP architecture with uniform embedment of δ-MnO2 nanoparticles and different adsorption efficiencies. δ-MnO2 loading was a linear function of the number of times the integrated procedure was repeated, underlying the accurate control of CDP recycling. Thus, this approach may represent a new method for the removal of aqueous micropollutants.