Comparing the influence of humic/fulvic acid and tannic acid on Cr(VI) adsorption onto polystyrene microplastics: Evidence for the formation of Cr(OH)3 colloids

Microplastics (MPs) can act as vectors for various contaminants in the aquatic environment. Although some research has investigated the adsorption characteristics and influencing factors of metals/organic molecules on MPs, the effects of dissolved organic matter (DOM) (which are ubiquitous active species in ecosystems) on metal oxyanions such as Cr(VI) capture by MPs are largely unknown. This study explored the adsorption behaviors and mechanisms of Cr(VI) oxyanions onto polystyrene (PS) MPs using batch adsorption experiments and multiple spectroscopic methods. The effects of representative DOM components (i.e., humic acid (HA), fulvic acid (FA) and tannic acid (TA)) on Cr(VI) capture by PS were particularly studied. Results revealed a significantly enhanced adsorption of Cr(VI) on PS in the presence of TA. The Cr(VI) adsorption capacity was increased from 2876 μg g to 4259 μg g and 5135 μg g when the TA concentrations raised from 0 to 10 and 20 mg L, respectively. Combined microscopic and spectroscopic investigations revealed that Cr(VI) was reduced to Cr(III) by TA and formed stable Cr(OH) colloids on PS surfaces. Contrarily, HA and FA inhibited Cr(VI) adsorption onto PS, especially at pH > 2.0 and higher DOM concentrations, due to site competition and electrostatic repulsion. Increase in pH was found to reduce zeta potentials of MPs, resulting in inhibited Cr(VI) adsorption. The adsorbed Cr(VI) declined with increasing ionic strength, implying that outer-sphere surface complexation affected the adsorption process in the presence of DOM. These new findings improved our fundamental understanding of the fate of Cr(VI) and MPs in DOM-rich environmental matrices.