1 College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai, 201306, China. zzhao@shou.edu.cn.
2 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China. zzhao@shou.edu.cn.
3 College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai, 201306, China.
4 Department of Chemistry and Biochemistry, Concordia University, Montreal, QC, H4B 1R6, Canada.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) have been frequently detected in groundwater globally. With the phase-out of perfluorooctane sulfonate (PFOS) and perfluorooctanate (PFOA) due to their risk to the ecosystem and human population, various novel PFASs have been used as replacements and detected in groundwater. In order to summarize the current understanding and knowledge gaps on PFASs in groundwater, we reviewed the studies about environmental occurrence, transport, and risk of legacy and novel PFASs in groundwater published from 1999 to 2021. Our review suggests that PFOS and PFOA could still be detected in groundwater due to the long residence time and the retention in the soil-groundwater system. Firefighting training sites, industrial parks, and landfills were commonly hotspots of PFASs in groundwater. More novel PFASs have been detected via nontarget analysis using high-resolution mass spectrometry. Some novel PFASs had concentrations comparable to that of PFOS and PFOA. Both legacy and novel PFASs can pose a risk to human population who rely on contaminated groundwater as drinking water. Transport of PFASs to groundwater is influenced by various factors, i.e., the compound structure, the hydrochemical condition, and terrain. The exchange of PFASs between groundwater and surface water needs to be better characterized. Field monitoring, isotope tracing, nontarget screening, and modeling are useful approaches and should be integrated to get a comprehensive understanding of PFASs sources and behaviors in groundwater.