In 2000-2002, three rangeland and six irrigated sites were instrumented to assess the storage and transit time of chemicals in thick (15 to 50 m) unsaturated zones (UZ) in the High Plains. These processes are likely to influence relations between land use and groundwater quality, yet they have not been documented systematically in the High Plains. Land use and climate were important controls on the size of subsoil chloride, nitrate, and pesticide compound reservoirs. The reservoirs under irrigated cropland generally were larger than those under rangeland because more chemicals were applied to cropland than to rangeland. In some cases, chloride and nitrate reservoirs under rangeland were larger than those under cropland, presumably because of long‐term evaporative concentration near the base of the root zone. Natural salts mobilized by irrigation return flow accounted for as much as 60 and 80% of the nitrate and chloride reservoirs, respectively, under some cropland, as indicated by detailed chemical profiles and isotopic tracers (¹⁵N, ¹⁸O in nitrate and ²H, ³H, ¹⁸O in water). Advective chemical transit times in the UZ under cropland ranged from about 50 to 375 years, longer than any of the instrumented fields had been irrigated, yet agrichemicals were detected at the water table at four of the six sites. The data provide evidence for the existence of slow and fast paths for water movement in the UZ, with larger subsoil chemical reservoirs occurring in areas dominated by slow paths. Implications of these findings with respect to water quality in the aquifer are significant because they indicate that the amount of chemical mass reaching the aquifer could increase with time as chemicals that still reside under irrigated fields reach the water table.