This dataset includes data collected to validate a method of analysis for arsenic species As(III), As(V), dimethylarsinate (DMA), and monomethylarsonate (MMA) in surface water and groundwater samples. It also includes site information and water chemistry for samples used in the validation and used for other studies of arsenic species in groundwater. It includes speciation data measured at multiple time points to establish or verify hold times and stability of As species in surface water and groundwater samples.