The marine microbial loop comprising picophytoplankton, bacteria and microzooplankton is essential in global carbon cycling, which is currently affected by anthropogenic pollutants. Nonetheless, the impact of anthropogenic pollutants on the marine microbial loop remains elusive. In this study, perfluorooctanoic acid (PFOA) and microplastics (MPs) were selected as representative anthropogenic pollutants to investigate their impacts on the marine microbial loop with Prochlorococcus MED4 (picophytoplankton), Alteromonas macleodii EZ55 (bacteria), Pseudocohnilembus persalinus and Cafeteria roenbergensis (microzooplankton) as model microorganisms. The picophytoplankton was identified to be most sensitive to PFOA with a sensitivity order of MED4 >
EZ55 >
C. roenbergensis >
P. persalinus. In contrast, polystyrene (PS) as a representative MP had less inhibition on the microbial loop, but synergistically magnified the inhibitive effects of PFOA on those four microorganisms. Moreover, PS significantly (p <
0.05) enhanced the bioconcentration and biomagnification of PFOA in the marine microbial loop, e.g., 1.89, 1.33, 1.22, and 2.18-fold increase in bioconcentration factor values in MED4, EZ55, P. persalinus and C. roenbergensis, respectively, compared to sole PFOA exposure. These results highlighted the exacerbated ecological risk of the co-existence of PFOA and MPs and provides the first insight into impacts of PFOA and PS on the marine microbial loop.