In this study, column tests using relatively uniform Jumunjin sand media were conducted to evaluate the feasibility of calcium polysulfide (CaS_x, CPS) in removing high concentration of Zn²⁺ in groundwater. The injected CPS solution reacted rapidly with Zn²⁺ in artificial groundwater and effectively reduced Zn²⁺ by more than 99% through metal sulfide precipitation. Since the density (d = 1.27 g/cm³) of CPS solution was greater than that of water, CPS solution settled down rapidly while capturing Zn²⁺ and formed stable CPS layer similar to dense nonaqueous phase liquid. Mass balance analysis on Zn²⁺ in CPS solution suggested that CPS solution effectively reacted with Zn²⁺ to form metal sulfide precipitates except for high groundwater seepage velocity of 400 cm/d. With greater groundwater seepage velocity, injected CPS did not completely dissolve at the CPS-water interface, but a partially-misible CPS layer continuously moved and reacted with Zn²⁺ in the direction of groundwater flow. Since hydraulic conductivity (K_h) decreased slightly due to the generated metal precipitates in the inter-pores of media, injection of CPS solution should be optimized to prevent clogging. As evidenced by both XRF and SEM/EDS results, ZnS precipitates were clearly observed through the reaction between the CPS solution and Zn²⁺. Further study is warranted to evaluate the feasibility of CPS to remove high-concentration heavy metal-contaminated groundwater in complex and heterogeneous media.

Keywords: Calcium polysulfide, Clogging, Column test, Heavy metal, Groundwater, Metal sulfide precipitation