Rainwater chemistry plays an important role in the earth-surficial ecosystem, but studies on rainwater chemical composition of karst agro-ecosystem are rare. To explore the rainwater alkalization and the provenance of components responsible for neutralization, two-years chemical monitoring of rainwater was carried out in a karst agricultural catchment in Southwest China. The main findings suggest that SO42-, NO3-, Ca2+, and NH(4)( )(+)are the principal ions. All the ionic contents show distinctly seasonal variation (highest in winter) in response to variations in seasonal precipitation because the rain-scour process can efficiently remove atmospheric materials. Source identification indicates that Cl- and Na+ are mainly derived from marine input whereas SO42+ and NO3- are controlled by anthropogenic emission, in particular, fixed emission sources. The source of NH4+ is attributed to intense agricultural production, while Ca2+ and Mg2+ are mainly derived from calcite dissolution. The rainwater alkalization caused by the seasonal acid neutralization (via basic components, Ca2+ and NH4+) is beneficial to crop growth but also reflect agricultural overfertilization. Sulfur controlled the total wet acid deposition (68%-94%) and could be a potential agent of weathering. (C) 2020 Elsevier Ltd. All rights reserved.