This study involved assessing and simulating the probable major pathways (surface and subsurface flow) and hydrogeochemical transport of arsenic (As) in the Beitou-Guandu area, Taiwan. A one-dimensional (1-D) generic, reactive, chemical transport model (PHREEQC) was adopted. The calibrated model showed that As transported to the downstream Guandu plain and Tan Shui river mouth accounted for 50.7 and approximately 100 % of the As in the subsurface flow pathway, respectively, suggesting that subsurface flow constituted a major As pathway. The highest As water concentration occurred near the Beitou geothermal valley because of the low pH and high redox potential in both the surface and subsurface pathways. However, As may be scavenged by aqueous Fe(II) in a reducing environment. The As concentrations in the downstream Guandu plain and Guandu wetland decreased as the simulated time increased, resulting in the adsorption of As on the surface of Fe oxydroxides and limiting the mobility of As in the surface flow pathway. The major retardation mechanism of As mobility in the subsurface flow pathway of the Guandu plain and Guandu wetland was governed by the adsorption reactions of iron-oxide and iron-sulfide minerals. The 1-D transport model was applied to predict the evolution of As in the subsurface flow pathway from 2013 to 2020. The results indicated that the As concentrations in all cells gradually increased. The geochemical redox reactions of As in the subsurface pathway subsequently led to the oxidization of As-bearing sulfides, causing As concentrations to rise substantially in the hillside area.