Arsenic is a pervasive pollutant in groundwater, affecting more than 100 million people in 50 countries, including China. Toxicological analysis of As is complicated because As exists in the environment in a variety of forms and redox states. Here, a thermodynamic equilibrium model was used to calculate As speciation, investigate pathways of As accumulation and assess the risk of adverse health effects from oral ingestion of dissolved As from shallow groundwater in the Poyang Lake area (China). The accumulation of As, Fe, and NH₄⁺ in the studied shallow groundwater was found to be the result of the dissolution of As-containing Fe, and probably Mn, (oxyhydr)oxides under reducing conditions due to excess influx of organic matter into the shallow aquifer. Modeling showed that As(III), which is more toxic than As(V), predominated at nearly all sampling sites, regardless of redox conditions. Arsenic tends to accumulate in the highest concentrations as neutral species (As(OH)₃⁰, HAsO₂⁰) under Eh<50 mV. In the lower reaches of the Ganjiang and Xiushui Rivers, an increased non-carcinogenic risk from oral ingestion of As from drinking water was observed. The elevated cancer risk was found to be present throughout the study area. The lower reaches of the Ganjiang and Xiushui Rivers that have been shown to have the highest risk of both non-carcinogenic and carcinogenic adverse health effects are associated with more toxic As(III) species. Given the As speciation and risk profile, it is recommended to introduce strategies to alter redox conditions in shallow groundwater by adopting safer irrigation practices and managing fertilizer applications to avoid the buildup of high As concentrations associated with adverse health effects.