Removal of cadmium and tetracycline by lignin hydrogels loaded with nano-FeS: Nanoparticle size control and content calculation.

Cadmium (Cd) and tetracycline (TC) cause serious environmental risks. Nanomaterials have been extensively applied for environmental remediation. The size and content of nanoparticles directly affect the removal of contaminants. However, size regulation and quantitative determination of nanoparticles cannot be easily realized. In this study, hydrogels with different polymerization degrees were prepared by adjusting the contents of acrylamide (AM) and sodium lignosulfonate polymeric monomers. Ferrous sulfide (FeS) nanoparticles of different sizes were synthesized in situ within the hydrogels. The nanoparticle size decreased from 600 to 200 nm with increasing hydrogel polymerization degree, and an incomplete crystalline state was observed at the highest polymerization degree. By combining energy dispersive spectroscopy (EDS) images with the maximum between-class variance (Otsu) method, the content of nanoparticles was calculated to be 7.81%, 15.05%, 22.62%, 27.10%, 21.97%, and 23.95%. The distribution state of FeS compounds was also obtained. A low polymerization degree resulted in high FeS dispersal, and a high polymerization degree affected the uniformity distribution based on irregular ion diffusion. The obtained nanocomposites with different polymerization degrees were applied to the removal of Cd and TC in water. The removal capacity for both contaminants revealed a trend of initially increasing and then decreasing. The initial increase was related to the increasing content and decreasing size of the FeS nanoparticles, while the following decrease was due to the decreasing content and incomplete crystallization of the FeS nanoparticles. Overall, changing the proportion of polymeric monomers is an effective way to regulate particle size, and the Otsu method combined with EDS mapping images is a feasible method for calculating the content of nanoparticles.

Adsorption mechanism of two pesticides on polyethylene and polypropylene microplastics: DFT calculations and particle size effects.

Polyethylene (PE) and polypropylene (PP) microplastics (MPs), as carriers, can bind with pesticides, which propose harmful impacts to aqueous ecosystems. Meanwhile, carbofuran and carbendazim (CBD), two widely used carbamate pesticides, are toxic to humans because of the inhibition of acetylcholinesterase activity. The interaction between two MPs and two pesticides could start in farmland and be maintained during transportation to the ocean. Herein, the adsorption behavior and mechanism of carbofuran and carbendazim (CBD) by PE and PP MPs were investigated via characterization and density functional theory (DFT) simulation. The adsorption kinetic and thermodynamic data were best described by pseudo-second-order kinetics and the Freundlich models. The adsorption behaviors of individual carbofuran/CBD on both MPs were very similar. The CBD adsorption rate and capacity of PE and PP MPs were higher than those of carbofuran. This phenomenon explained the lower negative effects of DOM (oxalic acid, glycine (Gly)) on CBD adsorption relative to those of carbofuran. The presence of oxalic acid and Gly decreased the PE adsorption by 20.40-48.02% and the PP adsorption by 19.27-42.11%, respectively. It indicated the significance of DOM in carbofuran cycling. The adsorption capacities were negatively correlated with MPs size, indicating the importance of specific surficial area. Fourier transformation infrared spectroscopy before and after adsorption suggested that the adsorption process did not produce any new covalent bond. Instead, intermolecular van der Waals forces were one of the primary adsorption mechanisms of carbofuran and CBD by MPs, as evidenced by DFT calculations. Based on the zeta potential, the electrostatic interaction explained the higher adsorption CBD by MPs than carbofuran.