The oxidation of sulfide minerals and pH-neutralization reactions in unsaturated mine waste rock produce changes in the pore-gas composition, leading to substantial deviations from atmospheric conditions. We studied the temporal and spatial changes in pore-gas composition, temperature, and volumetric water content (VWC) in an experimental pile during a 2-yr period. The pile was constructed by end dumping and is exposed to a marked two-season (wet-dry) climate. The grain-size segregation of waste rock occurring during end-dump construction significantly affected the spatial distribution of pore-gas composition within the pile. Results from continuous monitoring also demonstrated the role of VWC fluctuations on pore-gas composition at the study site. Oxygen decreased during the wet season, while CO 2 concentrations showed the opposite behavior. Gaseous diffusion was inferred as an important O 2 supply mechanism for this experimental waste-rock pile. In addition, wind-induced gas advection and convection probably contributed to O 2 ingress into the basal regions of the pile. Intrinsic oxidation rates were estimated based on one-dimensional reaction-diffusion modeling, showing pronounced variations between the top and bottom of the pile. These differences can be attributed to low reactivity in the basal region of the pile related to the coarse-grained nature of the material and the omission of O 2 -supply mechanisms other than diffusion. The results demonstrate the complex interactions between physical and chemical heterogeneities in mine waste rock and contribute to an improved understanding of oxidation reactions and metal release that occur in sulfidic waste rock.Abbreviations: TP, tipping phase; VWC, volumetric water content.Open-pit mining produces large amounts of waste rock containing variable amounts of sulfide minerals. This waste rock is deposited in storage facilities, under predominantly unsaturated conditions, where it can interact with water and O 2 derived from the atmosphere. Weathering of the sulfide minerals can lead to acid generation and metal release. The quality of the drainage depends strongly on the rate at which the sulfides are oxidized with time and the amount of pH-buffering minerals present in the system (Amos et al., 2015). Understanding the processes controlling metal release at the scale of operational facilities is required to make informed decisions for mine closure plans.Oxidation of sulfide minerals in mine waste generates acidity, liberating metals and releasing sulfate, which negatively affects the quality of the drainage water. The oxidation reactions consume O 2 derived from the atmosphere, and the O 2 availability within the pile provides a major control on the progress and extent of sulfide mineral weathering. For example, the oxidation of pyrite can be described as 22 2 22 4 FeS 3.5O H O 2H Fe 2SO ++ -Core Ideas • Grain-size segregation during end dumping affects the pore-gas distribution. • Seasonal variations in precipitation affect O 2 ingress and CO 2 egress. • Hot spots...