Patchy distribution of high As groundwater has normally been observed in As-affected areas. Spatial and temporal evolutions help in better understanding mechanisms of As mobilization and in developing effective strategies for ensuring drinking water safety. Four multilevel samplers were installed approximately along the groundwater flow path to investigate spatial and temporal variations in groundwater As in the Hetao basin, Inner Mongolia. Both water chemistry and groundwater level were monitored for about two years. Groundwater As concentration generally showed increasing trends, and Eh values showed decreasing trends along the flow path, indicating that As was mobilized via reductive dissolution of Fe oxides. However, in evaporation discharge area, shallow groundwater As was generally lower than those upstream and downstream. In addition to evaporation, siderite and pyrite precipitations controlled groundwater As concentrations. The negative correlations between As concentration and SI pyrite (or SI siderite ) implied that siderite and pyrite precipitations would scavenge groundwater As and lower As concentration. Temporal variation showed different trends in different locations. It may reflect replenishment of high/low As groundwater for the increase/decrease in As concentrations, resulting from water level fluctuation. The increase trends in groundwater As concentrations at depth around 15 m in the discharge areas would result from the increase in the recharge of underlying groundwater (20 m) with high As concentration due to enhanced evaporation in the seasons with high water levels. The investigation suggested that monitoring of groundwater As should be routinely carried out to ensure the drinking water safety in the As-affected areas.aquifer, water-rock interaction, hydrogeochemistry, As species, evaporation High As groundwater has posed a significant health impact on thousands of millions of people [1], which has received much concern from scientific community and management agencies [2][3][4][5]. Many investigations have shown that groundwater As is highly variable at both local and regional scale in reducing aquifers from river deltas (including Red River delta, Mekong delta, Ganges delta, Yellow river delta, Pearl River delta, etc.) [4,5] and inland basins (including the Hetao basin, the Datong basin, the Yinchuan basin, the west Jilin basin, and the Zhunger basin, etc.) [6][7][8][9][10][11]. Groundwater As concentrations span three orders of magnitude over distances from tens of meters to kilometers [6,[12][13][14][15]. The causes of the lateral heterogeneity in As concentration are diverse, including recharge of human-derived dissolved organic carbon (DOC) [4,16], distribution of natural organic matter [17,18], distribution of surface geologic conditions [8,[19][20][21], surface water-groundwater interaction [7], distribution of paleaosol layers [22][23][24], groundwater flushing [26,27], and recharge rate [20,25]. The patchy distribution of groundwater As makes it difficult to get safe drinking wa...