Adsorption mechanism of trace heavy metals on microplastics and simulating their effect on microalgae in river

Abstract

Microplastics (MPs) and heavy-metal contamination in freshwater is an increasing concern. Fe, Mn, Pb, Zn, Cr, and Cd are common heavy metals that can easily flow into rivers causing water pollution. Microplastics act as carriers for heavy metals and increase the transport of contaminants in freshwater systems. We investigated the adsorption mechanisms of three kinds of MPs having similar particle sizes, namely polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC), with respect to trace heavy metals of Pb, Cu, Cr, and Cd under different temperature and salinity conditions. The reaction kinetics of the adsorption of different trace heavy metals on different MPs were consistent with both the quasi primary and quasi secondary kinetic models, indicating the complexity of heavy metal adsorption by MPs. The adsorption rate of heavy metal on MPs was mainly controlled by intra-particle diffusion, and the isotherm model indicated that the adsorption of Pb, Cu, Cr, and Cd by MPs occurred in the form of monolayer physical adsorption. Additionally, an increase in temperature and decrease in salinity were favourable to improve the affinity of MPs toward heavy metals (through adsorption). Zeta potential measurements and Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that electrostatic force interaction was the main mechanism of the adsorption process; oxygen-containing functional groups, π-π interaction, and halogen bonds played important roles in the process of adsorption. Furthermore, the growth inhibition and oxidative stress of microalgae Chlorella vulgaris (GY-D27) due to PP, PS, and PVC were analysed; notably, MPs or Pb inhibited the growth of Chlorella vulgaris. However, the reduced toxicity to Chlorella vulgaris, with respect to a mixture of Pb and MPs, was confirmed using superoxide dismutase and catalase enzyme activities. Our results can be applied for the risk assessment of heavy metals and MPs in aquatic environments.

Keywords: Adsorption mechanism; Chlorella vulgaris; Growth inhibition; Microplastics; Trace heavy metals.